JP5786190B2 - Substrate processing method and substrate processing apparatus - Google Patents

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 is supplied to the substrate surface, and after freezing it, the substrate surface is cleaned by thawing and removing with a rinse solution. Executed.

  That is, in the apparatus described in Patent Document 1, the following steps are executed. First, a DIW liquid film is formed on the entire surface of the substrate by supplying DIW to the surface of the substrate. At this time, DIW also penetrates into the fine pattern gap formed on the substrate surface due to its fluidity. Subsequently, the supply of DIW is stopped, and low temperature nitrogen gas is supplied to the substrate surface to freeze the DIW. As a result, the DIW that has entered between the contaminant such as particles and the substrate surface becomes ice and expands so that the contaminant such as particles is separated from the substrate by a minute distance. Further, by expanding in a direction parallel to the surface of the substrate, particles fixed to the substrate are peeled off. As a result, the adhesion force between the substrate surface and contaminants such as particles is reduced, and furthermore, contaminants such as particles are detached from the substrate surface. Thereafter, by removing the ice on the substrate surface by thawing and rinsing with a rinsing liquid, contaminants such as particles can be efficiently removed from the substrate surface.

JP 2008-71875 A (FIG. 3)

  In recent years, patterns made of fine concavo-convex shapes formed on electronic components such as semiconductor devices and liquid crystal display devices have been further miniaturized, and the structure itself has become three-dimensional. And it has a complicated 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 contact area between the bottom surface of the convex portion and the substrate constituting the pattern is reduced, and the adhesive force between the convex portion of the pattern and the substrate is reduced. Further, the strength of the convex portion itself is also reduced. Therefore, there is a high possibility that damages such as collapse / peeling of the convex portions of the pattern and deformation of the space between the convex portions of the pattern occur even with a small external force.

  When the conventional cleaning method disclosed in Patent Document 1 is applied to a substrate on which such a fine pattern is formed, DIW supplied to the substrate is adjacent to each other with a minute interval due to its fluidity. Intrusion also occurs between the convex portions of the pattern to be formed, the inside of the three-dimensional cylindrical shape, etc., and the DIW including that portion is frozen and washed. In this prior art, particles are removed by using a force generated when DIW expands as ice, and 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 to the pattern.

  The present invention has been made in view of the above problems, and an object of the present invention is to provide a substrate processing method and a substrate processing apparatus that can clean a pattern having a fine and complicated shape without causing damage.

  In order to solve the above problems, the present invention provides a first solidification target liquid supply step for supplying a first solidification target liquid capable of forming a solidified body to a substrate on which a pattern is formed, and a first solidification target liquid is supplied. A solidified body can be formed on the formed substrate, has a freezing point at a temperature lower than the freezing point of the first solidification target liquid, and the volume change when the phase changes from liquid to solid is larger than the first solidification target liquid. Supplying a second solidification target liquid and removing the first solidification target liquid on the substrate excluding the inside of the pattern gap; and a second solidification target liquid and a second solidification target liquid A coagulation step for cooling and solidifying to a temperature below the freezing point of the target liquid; and a removal step for removing the first coagulation target liquid and the second coagulation target liquid.

  The present invention also includes a substrate holding unit that holds a substrate on which a pattern is formed, a first solidification target liquid supply unit that supplies a first solidification target liquid that can form a solidified body to the substrate, and a first solidification target. A solidified body can be formed on the substrate supplied with the target liquid, has a freezing point at a temperature lower than the freezing point of the first solidification target liquid, and the volume change when the phase changes from liquid to solid is the first solidification. A second coagulation target liquid supply unit configured to supply a second coagulation target liquid larger than the target liquid and remove the first coagulation target liquid on the substrate excluding the inside of the pattern gap; and a first coagulation target liquid and a second coagulation target liquid And a coagulation part that solidifies by cooling to a temperature below the freezing point of the second coagulation target liquid, and a removal part that removes the first coagulation target liquid and the second coagulation target liquid.

  In the invention (substrate processing method and substrate processing apparatus) configured as described above, after supplying the first solidification target liquid to the substrate, the second solidification target liquid is supplied and the first solidification target liquid is removed from the substrate surface. ing.

  However, the pattern formed on the substrate is fine, and the speed at which the second solidification target liquid enters the minute area inside the pattern gap is determined by the second solidification target liquid in the area other than the inside of the pattern gap. Slower than the rate at which the liquid is removed. Therefore, the duration of the step of supplying the second coagulation target liquid is continued for at least the time required for the second coagulation target liquid to remove the first coagulation target liquid in a region other than the inside of the pattern gap, so Only leave the first coagulation target liquid.

  The first solidification target liquid and the second solidification target liquid are cooled to a temperature below the freezing point of the second solidification target liquid with the second solidification target liquid supplied and the first solidification target liquid remaining only inside the pattern gap. And then solidify. Since the freezing point of the first solidification target liquid is higher than the freezing point of the second solidification target liquid, the first solidification target liquid is solidified before the second solidification target liquid is solidified.

  When the first solidification target liquid is solidified within the pattern gap, the solidification body of the first solidification target liquid and the pattern can be regarded as a lump (solid), and the pattern is structurally reinforced. Therefore, it is possible to counter the force (particularly, the force acting in parallel with the main surface of the substrate) due to the second solidification target liquid solidifying and expanding in the subsequent solidification step, and damage such as pattern peeling can be prevented.

  The volume change when the first solidification target liquid changes phase from liquid to solid is smaller than the volume change when the second solidification target liquid changes phase from liquid to solid. Even so, the stress applied to the pattern by the volume expansion due to the phase change is smaller than the second solidification target liquid. Therefore, the substrate can be cleaned while reinforcing the pattern while preventing damage to the pattern.

  Moreover, a 1st coagulation object liquid can be made into a substance soluble with respect to a 2nd coagulation object liquid.

  In the invention thus configured, a substance of a good solvent (the first coagulation target liquid is soluble in the second coagulation target liquid) is used as the second coagulation target liquid with respect to the first coagulation target liquid. Accordingly, the first solidification target liquid can be removed by dissolving the first solidification target liquid with the second solidification target liquid, and the first solidification target liquid can be quickly removed from the substrate.

  Further, as the first solidification target liquid supply step, the first solidification target liquid can be supplied at a temperature equal to or higher than the freezing point.

  In the invention thus configured, the first solidification target liquid is supplied at a temperature equal to or higher than the freezing point. Accordingly, the first solidification target liquid can be supplied to the substrate in a liquid state, and can be penetrated into the pattern gap as the first solidification target liquid flows.

  Moreover, after performing the high temperature 2nd solidification target liquid supply process which supplies the 2nd solidification target liquid of the temperature higher than the freezing point of the 1st solidification target liquid as a 2nd solidification target liquid supply process, the freezing point of the 1st solidification target liquid A low-temperature second coagulation target liquid supply step for supplying a lower temperature second coagulation target liquid can be performed.

  In the invention thus configured, after supplying the second solidification target liquid having a temperature higher than the freezing point of the first solidification target liquid to the substrate, the second solidification target liquid having a temperature lower than the freezing point of the first solidification target liquid is supplied. Supply. Thus, by supplying the second coagulation target liquid having a temperature higher than the freezing point of the first coagulation target liquid, the first coagulation target liquid is brought into a liquid state, and the first coagulation target liquid is dissolved in the second coagulation target liquid. The liquid in the first coagulation target liquid can be quickly removed by swirling it with the flow of the second coagulation target liquid. In addition, after supplying the second solidification target liquid having a temperature higher than the freezing point of the first solidification target liquid, the second solidification target liquid having a temperature lower than the freezing point of the first solidification target liquid is supplied. Cool to a temperature lower than the freezing point of the liquid to be solidified. Thereby, while solidifying the 1st solidification object liquid and reinforcing a pattern, the time which a subsequent coagulation process requires can be shortened.

  Moreover, the removal liquid in which the first coagulation target liquid is soluble can be used.

  In the invention configured as described above, a substance having a good solvent (the first coagulation target liquid is soluble in the second coagulation target liquid) is used as the removal liquid with respect to the first coagulation target liquid. Accordingly, the first solidification target liquid can be removed by dissolving the first solidification target liquid with the removal liquid, and the first solidification target liquid can be quickly removed from the substrate.

  Moreover, a removal process can supply the removal liquid of the temperature more than the freezing point of a 1st solidification object liquid.

  In the invention thus configured, by supplying a removal liquid having a temperature equal to or higher than the freezing point of the first solidification target liquid, both the first solidification target liquid and the second solidification target liquid can be melted, and the substrate surface These liquids can be removed immediately.

  According to this invention, after the first coagulation target liquid remains in the pattern gap and solidifies, the second coagulation target liquid in the part other than the inside of the pattern gap is coagulated. Thus, after the pattern is reinforced with the first solidification target liquid, the second solidification target liquid can be solidified, and the pattern can be protected from the stress caused by the solidification of the second solidification target liquid. Therefore, the substrate can be cleaned without damaging 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 part in the processing unit of FIG. 4, a drainage collection part, and an atmosphere interruption | blocking part. It is a figure which shows the structure of the 2nd coagulation object liquid supply part and removal part in the processing unit of FIG. It is a figure which shows the structure of the 2nd coagulation object liquid supply unit in the 2nd coagulation object liquid supply part of FIG. It is a figure which shows the structure of the removal liquid supply unit in the removal part of FIG. It is a figure which shows the structure of the 1st coagulation object liquid supply part in the processing unit of FIG. It is a figure which shows the structure of the 1st coagulation object liquid supply unit in the 1st coagulation object liquid supply part of FIG. It is a figure which shows the structure of the solidification part in the processing unit of FIG. It is a figure which shows the structure of the nitrogen gas supply unit for solidification in the solidification part of FIG. It is a figure which shows the structure of the rinse part and drying gas supply part in the processing unit of FIG. It is a flowchart which shows operation | movement of the substrate processing apparatus in 1st embodiment. It is a flowchart which shows operation | movement of the substrate processing apparatus in 2nd embodiment.

  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 pattern is formed is referred to as “front surface”, and the main surface on which the pattern 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, a space between adjacent convex portions separated by a minute interval, a three-dimensional cylinder, a rectangular column, or the like is referred to as a “pattern gap”.

  Embodiments of the present invention will be described below with reference to the drawings, taking a substrate processing apparatus used for processing a semiconductor substrate as an example. The present invention is not limited to the processing of semiconductor substrates, and can be applied 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 is used for 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 processing apparatus.

  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). An opening / closing mechanism 943 (see FIG. 3) for opening and closing a portion (not shown) is provided.

  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. Prepare. 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 is provided with eight processing units 91 and eight fluid boxes 92 each.

  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 cleaning processing 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 holds the substrate W having a pattern formed on the surface thereof substantially horizontally, accommodates the rotating substrate holder 11 and the substrate holder 11 inside, and scatters from the substrate holder 11 and the substrate W. A drainage collecting unit 21 that receives and exhausts objects and the like and a surface Wf of the substrate W held by the substrate holding unit 11 are arranged to face each other, and a space above the substrate surface Wf is blocked from outside air. And an atmosphere blocking unit 23.

  In addition, the processing unit 91 includes a first solidification target liquid supply unit 31 that supplies the first solidification target liquid to the surface Wf of the substrate W, and a second solidification target liquid that supplies the second solidification target liquid to the surface Wf of the substrate W. Supply portion 43, coagulation portion 35 for supplying and solidifying a low-temperature coagulation gas to the first and second coagulation target liquids on the surface Wf of the substrate W, and the first coagulation on the substrate surface Wf A removal unit 45 that supplies and removes the removal liquid to the coagulation target liquid and the second coagulation target liquid, a rinse part 51 that supplies a rinse liquid toward the substrate surface Wf and the substrate back surface Wb, and the substrate surface Wf and the substrate back surface A drying gas supply unit 55 that supplies a drying gas toward Wb to block the substrate surface Wf and the substrate back surface Wb from the outside air, and a control that controls the operation of each unit of the substrate processing apparatus 9 based on a cleaning program to be described later. Unit 97; Provided.

In the present embodiment, tertiary butanol (t-butanol) (chemical formula: C ₄ H ₁₀ O, freezing point: 25.6 ° C. (Celsius)), which is an organic solvent, is used as the first coagulation target liquid. Deionized water (De Ionized Water: hereinafter referred to as “DIW”) is used as the target liquid, the removal liquid, and the rinse liquid, respectively. In the present embodiment, nitrogen gas is used as the coagulation gas and the drying gas.

  Moreover, DIW which is the second coagulation target liquid is a good solvent (the first coagulation target liquid is soluble in the second coagulation target liquid) with respect to tertiary butanol which is the first coagulation target liquid.

  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.

  As described above, on the side of the side wall 901 that faces 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 is closed to close the inside of the processing unit 91. A shutter 911 is provided for maintaining the cleanliness of the atmosphere.

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

  First, the substrate holding unit 11 will be described. The base unit 111 of the substrate holding part 11 is fixed on the lower base member 903, and a disk-shaped spin base 113 having an opening at the center part is rotatably and substantially horizontally above the base unit 111. 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. Then, the control unit 97 issues an operation command to the substrate holding unit 11 to expand and contract the air cylinder of the substrate holding member drive mechanism 119. Thereby, each substrate holding member 115 is switched between a “closed state” in which the substrate holding portion presses the outer peripheral end surface of the substrate W and an “open state” in which the substrate holding portion is separated from the outer peripheral end surface of the substrate W. It is possible. 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 a closed state, each substrate holding member 115 holds the peripheral edge of the substrate W, and holds the substrate W in a substantially horizontal posture with 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 addition, a rotation shaft of a substrate rotation mechanism 121 including a motor is connected to the central shaft 117 of the substrate holding unit 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. Then, the control unit 97 issues an operation command to the substrate holding unit 11 to drive the substrate rotation mechanism 121. As a result, the spin base 113 fixed to the central axis 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 part 21 will be described. A substantially annular cup 210 is provided around the substrate holding unit 11 and above the lower base member 903 so as to surround the periphery of the substrate W held by the substrate holding unit 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 part 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. Then, the control unit 97 issues an operation command to the drainage collecting unit 21 to drive the guard lifting mechanism 217. Accordingly, the inner component member 211, the middle component member 213, and the outer component member 215 move in the vertical direction along the rotation center axis A1 independently or in synchronization with a plurality of members.

  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. That is, 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 part 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 processing, and are collected separately. It becomes possible to do. Therefore, by separating each liquid and discharging it to the 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 unit 23 will be described. The blocking member 231 that is a substrate facing member of the atmosphere blocking unit 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. Further, the diameter of the blocking member 231 is formed to be 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. Then, the control unit 97 issues an operation command to the atmosphere blocking unit 23 to drive the blocking member rotating mechanism 235. Accordingly, the blocking member 231 is rotated around the rotation center axis A5 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 rotation direction as the substrate W and at substantially the same rotation speed in accordance with the rotation of the substrate W held by the substrate holding unit 11. The spin base 113 and the blocking member 231 are arranged so that the rotation center axes A1 and A5 substantially coincide. Accordingly, the spin base 113 and the blocking member 231 rotate about the same rotation center axis.

  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 located on the outer side in the circumferential direction of the cup 210 of the drainage collecting unit 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. Then, the control unit 97 issues an operation command to the atmosphere blocking unit 23 and drives the blocking member lifting mechanism 247. Accordingly, the blocking member 231 is brought close to the spin base 113 and is separated away.

  That is, the control unit 97 controls the operation of the blocking member lifting / lowering mechanism 247 to raise the blocking member 231 to a separation position above the substrate holding unit 11 when loading / unloading the substrate W into / from the processing unit 91. On the other hand, when the substrate W is subjected to a rinsing process described later, drying of 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 holder 11. To lower.

  Next, the configuration of the second coagulation target liquid supply unit 43 and the removal unit 45 will be described with reference to FIG. FIG. 6 is a schematic diagram showing the configuration of the second coagulation target liquid supply unit 43 and the removal unit 45.

  The nozzle 411 that supplies the second solidification target liquid or the removal liquid to the surface Wf of the substrate W is supported by a nozzle driving 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.

  The control unit 97 issues an operation command to the nozzle drive mechanism 413 to drive the vertical drive unit 421. Thereby, the turning vertical axis 417 moves up and down, and the nozzle 411 attached to the arm 423 moves up and down. In addition, the control unit 97 issues an operation command to the nozzle drive mechanism 413 to drive the turning drive unit 419. As a result, the turning vertical axis 417 rotates about the rotation center axis A4 and the arm 423 is turned, so that the nozzle 411 attached to the arm 423 is swung.

  The nozzle 411 is connected to the second coagulation target liquid supply unit 433 and the removal liquid supply unit 453 via a collecting pipe 449 and pipes 435 and 455, respectively.

  FIG. 7 shows the configuration of the second coagulation target liquid supply unit 433. The second solidification target liquid supply unit 433 includes a DIW tank 441 for storing DIW, a pump 443 for pumping DIW from the DIW tank 441, a first temperature adjustment unit 445 for adjusting DIW to a first temperature, and a DIW for a second A second temperature adjustment unit 446 for adjusting the temperature and on-off valves 436 and 437 are configured. Note that the pipe 435 connected to the DIW tank 441 is once branched into a pipe 438 and a pipe 439, joined again, and connected to the nozzle 411.

  A pump 443 is inserted between the DIW tank 441 and the portion where the pipe 435 branches to pressurize and send the DIW. The DIW delivered from the pump 443 is branched and supplied to the pipes 438 and 439.

  The pipe 438 has a first temperature adjustment unit 445 for adjusting DIW to a first temperature and an on-off valve 436 for controlling the flow of DIW, and the pipe 439 has a second temperature adjustment unit for adjusting DIW to a second temperature. On-off valves 437 for controlling the flow of 446 and DIW are inserted respectively. Both the on-off valves 436 and 437 are normally closed. The on-off valves 436 and 437 are electrically connected to the control unit 97.

  When the control unit 97 issues an operation command to the second coagulation target liquid supply unit 43 and opens the on-off valve 436, DIW is pressurized by the pump 443 from the DIW tank 441 and sent to the first temperature adjustment unit 445. The DIW sent to the first temperature adjustment unit 445 is adjusted to the first temperature and supplied to the substrate surface Wf via the pipe 438, the pipe 435, the collective pipe 449, and the nozzle 411.

  Further, when the control unit 97 issues an operation command to the second coagulation target liquid supply unit 43 and opens the on-off valve 437, DIW is pressurized from the DIW tank 441 by the pump 443 and sent to the second temperature adjustment unit 446. . The DIW sent to the second temperature adjustment unit 446 is adjusted to the second temperature and supplied to the substrate surface Wf via the pipe 439, the pipe 435, the collective pipe 449, and the nozzle 411.

  Here, the first temperature adjustment unit 445 and the second temperature adjustment unit 446 may use known temperature adjustment means such as a temperature adjustment device using a Peltier element, a heat exchanger using water, oil, hydrofluorocarbon, or the like. . Further, the DIW tank 441 may not be provided in the second coagulation target liquid supply unit 433, and DIW may be directly supplied from the factory utility side. Note that the pump 443 of the second coagulation target liquid supply unit 433 always operates from the time when the substrate processing apparatus 9 is activated.

  The second solidification target liquid supply unit 433, the pipe 435, the collective pipe 449, the nozzle 411, and the nozzle drive mechanism 413 constitute the second solidification target liquid supply unit 43.

  Returning to FIG. An open / close valve 457 is inserted in the pipe 455, and the open / close valve 457 is normally closed. The on-off valve 457 is electrically connected to the control unit 97. Then, the control unit 97 issues an operation command to the removal unit 45 and opens the on-off valve 457. As a result, the removal liquid is supplied from the removal liquid supply unit 453 to the substrate surface Wf via the pipe 455, the collective pipe 449 and the nozzle 411. The removal liquid supply unit 453 may be provided inside the substrate processing apparatus 9 or may be provided outside.

  FIG. 8 shows the configuration of the removal liquid supply unit 453. The removal liquid supply unit 453 includes a DIW tank 461 that stores DIW, a pump 463 that pumps DIW from the DIW tank 461, and a temperature adjustment unit 465 that adjusts the temperature of the DIW. The pump 463 connected to the DIW tank 461 pressurizes DIW and sends it to the temperature adjustment unit 465. The DIW supplied to the temperature adjustment unit 465 via the pump 463 is adjusted to a predetermined temperature by the temperature adjustment unit 465 and supplied to the substrate surface Wf via the pipe 455, the collective pipe 449 and the nozzle 411.

  Here, the temperature adjustment unit 465 may be a known temperature adjustment means such as a temperature adjustment device using a Peltier element or a heat exchanger using water, oil, hydrofluorocarbon or the like. Further, the DIW tank 461 may not be provided in the removal liquid supply unit 453, and DIW may be directly supplied from the factory utility side. The pump 463 of the removal liquid supply unit 453 is always operating from the time when the substrate processing apparatus 9 is activated.

  The removal liquid supply unit 453, the pipe 455, the collective pipe 449, the on-off valve 457, the nozzle 411, and the nozzle drive mechanism 413 constitute the removal unit 45.

  Next, the structure of the 1st coagulation object liquid supply part 31 is demonstrated using FIG. FIG. 9 is a schematic diagram showing the configuration of the first coagulation target liquid supply unit 31. The nozzle 311 for supplying the first solidification target 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.

  The control unit 97 issues an operation command to the first coagulation target liquid supply unit 31 and drives the vertical drive unit 321. Thereby, the turning vertical axis 317 moves up and down, and the nozzle 311 attached to the arm 323 moves up and down. In addition, the control unit 97 issues an operation command to the first coagulation target liquid supply unit 31 to drive the turning drive unit 319. As a result, the turning vertical axis 317 rotates about the rotation center axis A <b> 2, and the arm 323 is turned to swing the nozzle 311 attached to the arm 323.

  The nozzle 311 is connected to the first coagulation target liquid supply unit 333 via a pipe 335. An open / close valve 337 is inserted in the pipe 335, and the open / close valve 337 is normally closed. The on-off valve 337 is electrically connected to the control unit 97. Then, the control unit 97 issues an operation command to the first coagulation target liquid supply unit 31 and opens the on-off valve 337. As a result, the first solidification target liquid is supplied from the first solidification target liquid supply unit 333 to the substrate surface Wf via the pipe 335 and the nozzle 311. The first solidification target liquid supply unit 333 may be provided inside the substrate processing apparatus 9 or may be provided outside.

  FIG. 10 shows the configuration of the first coagulation target liquid supply unit 333. The first coagulation target liquid supply unit 333 includes a first coagulation target liquid tank 341 that stores the first coagulation target liquid, a temperature adjustment unit 345 that adjusts the temperature of the first coagulation target liquid, and a first coagulation target liquid tank 341. It is comprised with the pressurization part 344 which pressurizes and sends out the 1st solidification object liquid.

  A temperature adjustment unit 345 is provided in the first solidification target liquid tank 341, and a heat exchange pipe 347 extending from the temperature adjustment unit 345 is immersed in the first solidification target liquid stored in the first solidification target liquid tank 341. Has been. 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 is adjusted to a temperature higher than the freezing point (25.6 ° C. (degrees Celsius)) of the first solidification target liquid in order to melt the first solidification target liquid into a liquid. Heat exchange with the first solidification target liquid in the solidification target liquid tank 341 is performed to adjust the temperature of the first solidification target liquid.

  The temperature adjustment unit 345 is further provided with a stirring unit 349 for stirring the first solidification target liquid in the first solidification target liquid tank 341. The stirring unit 349 is provided with a propeller-shaped stirring blade at the tip of the rotating shaft (the lower end of the stirring unit 349 in FIG. 10), and the first solidification target liquid is stirred by rotating the stirring blade so that the entire temperature is uniform. Turn into.

  The pressurizing unit 344 includes a nitrogen gas tank 342 that is a gas supply source that pressurizes the first coagulation target liquid tank 341, a pump 343 that pressurizes the nitrogen gas, and a pipe 336. The nitrogen gas tank 342 is connected to the first solidification target liquid tank 341 by a pipe 336, and a pump 343 is inserted in the pipe 336.

  An atmospheric pressure sensor (not shown) is provided in the first coagulation target liquid tank 341 and is electrically connected to the control unit 97. The control unit 97 controls the operation of the pump 343 based on the value detected by the atmospheric pressure sensor, thereby maintaining the atmospheric pressure in the first coagulation target liquid tank 341 at a predetermined atmospheric pressure higher than the atmospheric pressure. Thereby, when the control unit 97 issues an operation command to the first coagulation target liquid supply unit 31 and opens the on-off valve 337, the first coagulation target liquid is pushed out from the pressurized first coagulation target liquid tank 341. And discharged from the nozzle 311 through the pipe 335. In addition, since the 1st solidification object liquid tank 341 supplies a 1st solidification object liquid using the atmospheric pressure by nitrogen gas as mentioned above, it is preferable to be comprised airtight.

  The first solidification target liquid sent from the first solidification target liquid supply unit 333 to the nozzle 311 is cooled by the atmosphere outside the pipe 335 in the pipe 335 on the way, and the flow rate of the first solidification target liquid discharged from the nozzle 311. There is a possibility that the temperature becomes unstable or the inside of the pipe 335 or the nozzle 331 is solidified and cannot be discharged from the nozzle 311 itself.

  Therefore, it is preferable to keep the temperature of the first coagulation target liquid in the path from the first coagulation target liquid supply unit 333 to the nozzle 311. That is, it is preferable to use a known heat insulation method such that the pipe 335 is a heat insulating pipe integrated with the heat insulating material or a vacuum heat insulating pipe, and a heat insulating material such as foamed polyethylene is attached to the pipe 335 for heat insulation. In addition, the pipe 335 is made into a double pipe, the heated gas or liquid is circulated in the outer pipe, and a heater such as a cable heater or a silicon rubber heater is attached to the pipe 335. It is further preferable to maintain the temperature of

  The method for adjusting the temperature of the first coagulation target liquid is not limited to the above-described method, and a method for adjusting the temperature of the wall surface of the first coagulation target liquid tank 341 or a unit of a Peltier element instead of the heat exchange pipe 347. A known temperature adjusting method such as a method of adjusting the temperature by immersing the substrate can be used.

  In addition, the method for making the temperature of the first coagulation target liquid in the first coagulation target liquid tank 341 uniform is not limited to the above-described method, and a method of separately circulating a first coagulation target liquid by providing a circulation pump. For example, a known method can be used.

  Next, the configuration of the solidifying part 35 will be described with reference to FIG. FIG. 11 is a schematic diagram showing the configuration of the solidifying part 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.

  The control unit 97 issues an operation command to the coagulation unit 35 and drives the vertical drive unit 361. Thereby, the turning vertical axis 357 moves up and down, and the nozzle 351 attached to the arm 363 moves up and down. In addition, the control unit 97 issues an operation command to the coagulation unit 35 to drive the turning drive unit 359. As a result, the turning vertical axis 357 rotates around the central axis A3 and the arm 363 is turned, so that the nozzle 351 attached to the arm 363 is swung.

  The nozzle 351 is connected to a solidification nitrogen gas supply unit 373 through a pipe 375. The solidification nitrogen gas supply unit 373 is electrically connected to the control unit 97. The solidification nitrogen gas supply unit 373 supplies nitrogen gas having a temperature lower than the freezing point of the second solidification target liquid to the substrate surface Wf via the pipe 375 and the nozzle 351. The solidification nitrogen gas supply unit 373 may be provided inside or outside the substrate processing apparatus 9.

  FIG. 12 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.

  The container 627 of the gas cooling unit 611 has a tank shape so that liquid nitrogen can be stored therein, and is capable of withstanding the temperature of liquid nitrogen (− (minus) 195.8 ° C. (degrees Celsius)), for example, glass, quartz Or it is formed by HDPE (High Density Polyethylene: 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. 12) 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. Further, the other end of the heat exchange pipe 629 (the side protruding above the container 627 in FIG. 12) 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.

  The control unit 97 issues an operation command to the coagulation unit 35, and opens the mass flow controller 625 so that a predetermined flow rate is obtained. Thereby, nitrogen gas is supplied from the nitrogen gas tank 619 to the heat exchange pipe 629 in the gas cooling unit 611 and is cooled by the cold heat of the liquid nitrogen stored in the container 627 while passing through the heat exchange pipe 629. Nitrogen gas cooled while passing through the heat exchange pipe 629 is supplied to the nozzle 351 through the pipe 375.

  A minute space is provided between the other end of the heat exchange pipe 629 (the side protruding above the container 627 in FIG. 12) and the container 627, and the exhaust pipe 631 extends from the space inside the container 627. The communication channel that leads to is formed. 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 are not provided in the solidification nitrogen gas supply unit 373, and it is possible to supply liquid nitrogen and nitrogen gas from the factory utility side. The solidification nitrogen gas supply unit 373 may be provided inside or outside the substrate processing apparatus 9.

  Next, the structure of the rinse part 51 and the gas supply part 55 for drying is demonstrated using FIG. FIG. 13 is a schematic diagram showing the configuration of the rinse section 51 and the drying gas supply section 55. The rinsing unit 51 supplies a rinsing liquid toward the substrate surface Wf and the substrate back surface Wb, and the drying gas supply unit 55 supplies a drying gas toward the substrate surface Wf and the substrate back surface Wb.

  First, the pipe line 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 aforementioned blocking member rotating mechanism 235 of the atmosphere blocking portion 23 to the opening of the central portion of the blocking member 231, and the upper first supply tube 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. A lower first supply pipe 281 is inserted into a communication space from the upper surface of the spin base 113 of the substrate holding unit 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 rinse part 51 is demonstrated. The rinsing unit 51 supplies the rinsing liquid from the rinsing liquid supply unit 513, which is a rinsing liquid supply source, to the substrate front surface Wf and the substrate back surface Wb, respectively. One end of a main pipe 515 is connected to a rinse liquid 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. Further, the pump of the rinsing liquid supply unit 513 always operates from the time when the substrate processing apparatus 9 is activated.

  An open / close valve 519 is inserted in the upper branch pipe 517. The on-off valve 519 is always closed. The on-off valve 519 is electrically connected to the control unit 97. Then, the control unit 97 issues an operation command to the rinsing unit 51 and opens the on-off valve 519. Thus, the rinse liquid is supplied from the rinse liquid supply unit 513 to the substrate surface Wf via the main pipe 515, the upper branch pipe 517, the upper second supply pipe 273 and the nozzle 275.

  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. Then, the control unit 97 issues an operation command to the rinse unit 51 to open the on-off valve 523. Thus, the rinse liquid is supplied from the rinse liquid supply unit 513 to the substrate back surface Wb through the main pipe 515, the lower branch pipe 521, the lower second supply pipe 283, and the nozzle 291.

  This rinse liquid 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 nozzle Reference numeral 291 constitutes a rinse section 51. The rinsing liquid supply unit 513 may be provided inside or outside the substrate processing apparatus 9.

  Next, the drying gas supply unit 55 will be described. The drying gas supply unit 55 supplies the drying nitrogen gas to the substrate surface Wf and the substrate back surface Wb from the drying nitrogen gas supply unit 553 which 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, the control unit 97 issues an operation command to the drying gas supply unit 55 and opens the mass flow controller 559 so that the flow rate becomes a predetermined flow rate. Thus, room temperature nitrogen gas is supplied to the substrate surface Wf via the main pipe 555, the upper branch pipe 557, and the space between the inner surface of the upper first supply pipe 271 and the outer surface of the upper second supply pipe 273.

  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, the control unit 97 issues an operation command to the drying gas supply unit 55 and opens the mass flow controller 563 so that the flow rate becomes a predetermined flow rate. Thus, room temperature nitrogen gas is supplied to the substrate back surface Wb through the space between the inner surface of the main pipe 555, the lower branch pipe 561, and the lower first supply pipe 281 and the outer surface of the lower second supply pipe. The

  The drying nitrogen gas supply unit 553, main pipe 555, upper branch pipe 557, lower branch pipe 561, mass flow controller 559, mass flow controller 563, upper first supply pipe 271 and lower first supply pipe 281 are for drying. The gas supply part 55 is comprised. 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. Provide a disc. In the magnetic disk, the cleaning conditions corresponding to the substrate W are stored in advance as a cleaning program (also called a recipe). The CPU reads the contents into the RAM, and the CPU executes the substrate according to the contents of the cleaning program read into the RAM. Each part of the processing device 9 is controlled. The control unit 97 is connected to an operation unit 971 (see FIG. 1) used for creating / changing a cleaning program and selecting a desired one from a plurality of cleaning programs.

  Next, the cleaning processing operation in the substrate processing apparatus 9 configured as described above will be described with reference to FIG. FIG. 14 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 has substantially the same number of rotations 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 cleaning 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 control unit 97 issues an operation command and performs the following operation.

  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 part 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 unit 11 brings the substrate holding member 115 into an open state.

  In addition, the first solidification target liquid supply unit 31 retreats the nozzle 311, the coagulation unit 35 retreats the nozzle 351, and the second solidification target liquid supply unit 43 retreats the nozzle 411 (each nozzle is disengaged outward in the circumferential direction of the cup 210 Move to the current position). Further, the on-off valves 337, 436, 437, 457, 519 and 523 are closed. Further, the mass flow controllers 559, 563, and 625 are set to a flow rate of 0 (zero).

  After the preparation for loading the substrate W into the processing unit 91 is completed, a substrate loading step (step S101) for loading 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 portion 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 to bring it out of the processing unit 91 and closes the shutter 911.

  When an unprocessed substrate W is loaded into the processing unit 91 and placed on the substrate support portion of the substrate holding member 115, the control unit 97 issues an operation command to the substrate holding portion 11, and the substrate holding member 115 is moved. Closed.

  After the unprocessed substrate W is held by the substrate holder 11, a first solidification target liquid supply step (step S102) for supplying tertiary butanol, which is the first solidification target liquid, is performed on the substrate surface Wf. First, the control unit 97 issues an operation command to the substrate holding unit 11, starts the rotation of the spin base 113, and maintains it during the first coagulation target liquid supply process. Further, the control unit 97 issues an operation command to the drainage collecting unit 21 to position the cup 210 at the middle collection position. Note that the blocking member 231 of the atmosphere blocking unit 23 maintains the separated position.

  The number of rotations of the substrate W in the first solidification target liquid supply step is preferably 300 to 1000 rpm so that the tertiary butanol supplied to the substrate surface Wf can diffuse over the entire surface of the substrate surface Wf. Below, the rotation speed of the board | substrate W in a 1st solidification object liquid supply process is demonstrated as 500 rpm.

  Further, the control unit 97 issues an operation command to the first coagulation target liquid supply unit 31 to position the nozzle 311 near the center of the substrate surface Wf. After the positioning of the nozzle 311 is completed, the control unit 97 issues an operation command to the first coagulation target liquid supply unit 31 and opens the on-off valve 337. As a result, tertiary butanol is supplied from the first coagulation target liquid supply unit 333 to the vicinity of the center of the substrate surface Wf via the pipe 335 and the nozzle 311.

  The tertiary butanol is preferably supplied in a liquid state to the substrate surface Wf. In the present embodiment, the tertiary butanol is heated in the first solidification target liquid tank 341 by the temperature adjustment unit 345 at a temperature not lower than the freezing point (25.6 ° C. (degrees Celsius)) and not higher than the boiling point (82.5 ° C. (degrees Celsius)). Adjust to supply. In addition, in order to shorten the time which solidifies tertiary butanol by the below-mentioned low temperature 2nd solidification object liquid supply process, it is preferable that the temperature of tertiary butanol is low temperature more than a freezing point. In the following description, the temperature of tertiary butanol is assumed to be 30 ° C. (Celsius).

  Tertiary butanol 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 tertiary butanol flows, the tertiary butanol penetrates into the pattern gap formed on the substrate surface Wf.

  After tertiary butanol diffuses over the entire surface Wf of the substrate, the control unit 97 issues an operation command to the first coagulation target liquid supply unit 31 and closes the on-off valve 337. In addition, the control unit 97 issues an operation command to the first coagulation target liquid supply unit 31 to position the nozzle 311 to the retracted position (a position where the nozzle 311 is out of the cup 210 in the circumferential direction).

  Next, a high temperature second coagulation target liquid supply step (step S103) is performed for supplying DIW, which is the second coagulation target liquid at the first temperature, to the substrate surface Wf to which the tertiary butanol is adhered. First, the control unit 97 issues an operation command to the drainage collection unit 21 to position the cup 210 at the external collection position. The rotation of the substrate W maintains the same rotation speed as that in the first solidification target liquid supply process. Further, the blocking member 231 of the atmosphere blocking unit 23 maintains the separated position.

  In addition, the control unit 97 issues an operation command to the second coagulation target liquid supply unit 43, and positions the nozzle 411 above the vicinity of the center of the substrate surface Wf. After the positioning of the nozzle 411 is completed, the control unit 97 issues an operation command to the second coagulation target liquid supply unit 43 to open the on-off valve 436. Thus, the DIW is adjusted to the first temperature by the first temperature adjustment unit 445 and supplied to the vicinity of the center of the substrate surface Wf via the pipe 438, the pipe 435, the collective pipe 449, and the nozzle 411. Hereinafter, the first temperature DIW is referred to as “high temperature DIW”.

  The high temperature DIW causes tertiary butanol to be swept away from the substrate in a liquid state, so that the first of the tertiary butanol freezing point (25.6 ° C. (Celsius)) to the boiling point (82.5 ° C. (Celsius)) or less It is preferable to supply it after adjusting the temperature. In the following description, the temperature of the high temperature DIW is assumed to be 30 ° C. (Celsius).

  The high-temperature DIW supplied to the vicinity of the center of the substrate surface Wf is the first solidification target liquid that adheres 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 pushing away. Moreover, since tertiary butanol is easy to melt | dissolve in DIW, it is removed from the board | substrate surface Wf also by melt | dissolving in high temperature DIW.

  However, the pattern formed on the substrate surface Wf is fine, and the speed at which the high temperature DIW penetrates into the minute area inside the pattern gap is such that the high temperature DIW pushes tertiary butanol away or dissolves in the area other than the inside of the pattern gap. And much slower than removing. Accordingly, the time for performing the high temperature second coagulation target liquid supplying step is set to the time required for the high temperature DIW to wash away or dissolve the tertiary butanol in a region other than the inside of the pattern gap, thereby forming the substrate surface Wf. Tertiary butanol can be left only inside the formed pattern gap.

  In the subsequent low-temperature second solidification target liquid supply step, the amount of tertiary butanol that is pushed away by the second temperature DIW supplied to the substrate surface, dissolved, and removed is taken into consideration, and the high-temperature second solidification target The time for which the liquid supply process is continued may be shorter than the time during which tertiary butanol can be completely removed from the region other than the inside of the pattern gap.

  The high temperature DIW flushes or dissolves and removes the tertiary butanol in the region other than the inside of the pattern gap, and after leaving the tertiary butanol only in the inside of the pattern gap, the control unit 97 performs the second coagulation target liquid supply unit 43. The operation command is issued, and the on-off valve 436 is closed.

  Next, a low temperature second solidification target liquid supplying step (step S104) for supplying DIW at the second temperature to the substrate surface Wf is performed. First, the control unit 97 issues an operation command to the substrate holding unit 11 to change the rotation speed of the spin base 113 and maintain it during the low temperature second solidification target liquid supplying step. In addition, the cup 210 of the drainage collecting part 21 is maintained at the outside collecting position, and the blocking member 231 of the atmosphere blocking part 23 is maintained at the separated position.

  The rotation speed of the substrate W in the low-temperature second solidification target liquid supply step is such that DIW of the second temperature supplied to the substrate surface Wf diffuses over the entire surface of the substrate Wf and forms a liquid film stably on the substrate surface Wf. It is preferable to set it as 300-500 rpm so that it is possible. Below, the rotation speed of the board | substrate W in a low temperature 2nd solidification object liquid supply process is demonstrated as 400 rpm.

  Next, the control unit 97 issues an operation command to the second coagulation target liquid supply unit 43 to open the on-off valve 437. Thus, the DIW is adjusted to the second temperature by the second temperature adjustment unit 446 and supplied to the vicinity of the center of the substrate surface Wf via the pipe 439, the pipe 435, the collective pipe 449, and the nozzle 411. Hereinafter, the second solidification target liquid at the second temperature is referred to as “low temperature DIW”.

  Here, the low temperature DIW is adjusted to a second temperature lower than the freezing point of tertiary butanol (25.6 ° C. (Celsius)) in order to cool and solidify the tertiary butanol. In order to shorten the time for solidifying DIW in the solidification step described later, the low temperature DIW liquid is preferably at a temperature not lower than the freezing point of DIW and close to the freezing point of DIW. In the following description, the temperature of the low temperature DIW is assumed to be 0.5 ° C. (Celsius).

  The low temperature DIW supplied to the vicinity of the center of the substrate surface Wf pushes away the high temperature DIW existing on 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. While flowing.

  The low-temperature DIW supplied to the substrate surface Wf and flowing while spreading over the entire substrate surface Wf cools the substrate W and the tertiary butanol inside the pattern gap. The tertiary butanol inside the pattern gap solidifies when its temperature falls below the freezing point.

  The solid body of tertiary butanol solidified by remaining in a minute area inside the pattern gap can be regarded as a lump (solid) integrated with the pattern, and the pattern is structurally reinforced. Therefore, it is possible to counter a force (particularly a force acting in parallel with the substrate surface Wf) due to the solidification and expansion of DIW in a solidification process described later, and it is possible to prevent damage such as pattern peeling.

  A normal substance decreases in volume (increases density) as the temperature decreases, that is, it has a positive expansion coefficient with respect to temperature. On the other hand, water exhibits a positive expansion coefficient at 4 ° C. (degrees Celsius) or higher, but has a negative expansion coefficient (the volume increases (the density decreases) as the temperature decreases) below that. In particular, it expands greatly when water undergoes phase transition to ice. This is because the crystal structure of ice has a unique structure in which there are only four other water molecules (four-coordinate) around one water molecule. In other words, the structure is a tetrahedron-like structure in which four adjacent molecules are connected by hydrogen bonds around a single water molecule.

  This four-coordinate structure has the smallest coordination number among all the crystals, and has the largest intermolecular space. For this reason, the volume increases (density decreases) as compared with liquid water that does not have such a regular arrangement structure.

In contrast, tertiary butanol is density at 0.786 g / cm ³ in a liquid state, in the solid state is 0.79 g / cm ^3. That is, the density of the solid is greater than that of the liquid, and the volume decreases when the phase changes from liquid to solid.

  That is, comparing the volume changes when the DIW as the second coagulation target liquid and the tertiary butanol as the first coagulation target liquid undergo a phase change from liquid to solid, the tertiary butanol is smaller. Therefore, even if tertiary butanol solidifies in the pattern gap, the stress applied to the surrounding pattern is small, and damage such as pattern peeling does not occur.

  The high temperature second coagulation target liquid supply step and the low temperature second coagulation target liquid supply step constitute the second coagulation target liquid supply step.

  In the present embodiment, DIW adjusted to different temperatures in the high temperature second coagulation target liquid supply step and the low temperature second coagulation target liquid supply step is alternatively discharged. It is also possible to change the temperature of DIW supplied to the substrate surface Wf by simultaneously discharging and mixing them in the pipe 435 while adjusting the respective flow rates.

  After the tertiary butanol in the pattern gap is solidified, the control unit 97 issues an operation command to the second coagulation target liquid supply unit 43 and closes the on-off valve 437. Further, the control unit 97 issues an operation command to the second coagulation target liquid supply unit 43 to position the nozzle 411 at the retracted position (position where the nozzle 411 is disengaged from the outer side in the circumferential direction of the cup 210).

  Next, a solidification step (step S105) for solidifying the DIW liquid film formed on the substrate surface is performed. First, the control unit 97 issues an operation command to the substrate holder 11 to change the rotation speed of the spin base 113 and maintain it during the solidification process. It is desirable that the rotation speed of the substrate W in the coagulation step is rotated at a rotation speed of 30 to 100 rpm so that the DIW liquid film 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. In addition, the control unit 97 issues an operation command to the drainage collection unit 21 to position the cup 210 at the internal collection position. Note that the blocking member 231 of the atmosphere blocking unit 23 is maintained in the separated position.

  In addition, the control unit 97 issues an operation command to the coagulation unit 35 to position the nozzle 351 above the center of the substrate surface Wf. After the positioning of the nozzle 351 is completed, the control unit 97 issues an operation command to the coagulation unit 35, and nitrogen gas, which is a coagulation gas adjusted to a temperature lower than the solidification point of DIW (0 ° C. (degrees Celsius)), is supplied to the nozzle 351. From near the center of the substrate surface Wf.

  As will be described later, nitrogen gas is discharged from a nozzle 351 that moves from the vicinity of the center of the substrate W to the upper end of the substrate W over the surface Wf of the rotating substrate W to cool DIW and tertiary butanol on the substrate surface Wf. For this reason, the amount of cold supplied per unit area on the substrate W is limited. Moreover, it is preferable that the temperature of nitrogen gas is adjusted to −50 ° C. to − (minus) 190 ° C. (degrees Celsius) in consideration of the efficiency of cooling liquids and solids with gas and the endotherm from the atmosphere. In the following description, it is assumed that the temperature of the nitrogen gas is adjusted to − (minus) 190 ° C. (Celsius).

  After the discharge of nitrogen gas from the nozzle 351 is started, the control unit 97 issues an operation command to the coagulation unit 35, and the nozzle 351 is swung from the vicinity of the center of the substrate surface Wf to the vicinity of the periphery of the substrate surface Wf. 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 nitrogen gas over the entire surface of the substrate Wf. It is possible to uniformly form a DIW solidified body on the entire surface.

  DIW increases in volume by solidifying into ice (when water at 0 ° C. (Celsius) becomes ice at 0 ° C. (Celsius), its volume increases approximately 1.1 times). 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. Thereby, the ice which is a solidified body of DIW is removed and particles and the like are also removed together by a removing process which will be described later.

  As mentioned above, since tertiary butanol remains in the minute area inside the pattern gap and solidifies, it can be regarded as a lump (solid) integrated with the pattern, and the pattern is structurally It is reinforced. Therefore, it is possible to maintain the state where the DIW is solidified to be fixed on the substrate surface Wf against the force due to solidification and volume expansion, and damage such as peeling of the pattern from the substrate surface Wf does not occur.

  The swivel movement of the nozzle 351 not only moves once from the vicinity of the center of the substrate surface Wf to the vicinity of the periphery of the substrate surface Wf, but also repeats the movement from the vicinity of the center to the vicinity of the periphery several times. The reciprocation may be performed between the sky near the center and the sky near the periphery.

  After the DIW solidified body is formed on the entire surface of the substrate Wf, the control unit 97 issues an operation command to the solidifying section 35 and stops the supply of nitrogen gas. In addition, the control unit 97 issues an operation command to the coagulation unit 35 and positions the nozzle 351 to the retracted position (a position where the nozzle 351 is out of the cup 210 in the circumferential direction).

  Next, a removal step (step S106) is performed to remove the DIW solidified body formed on the substrate surface Wf and the tertiary butanol solidified body remaining in the pattern gap. First, the control unit 97 issues an operation command to the substrate holder 11 to change the rotation speed of the spin base 113 and maintain it during the removal process. Note that the cup 210 is maintained at the internal collection position, and the blocking member 231 of the atmosphere blocking section 23 is maintained at the separated position.

  The number of rotations of the substrate W in the removal process is such that DIW, which is the removal liquid supplied to the substrate surface Wf, can diffuse over the entire surface of the substrate surface Wf, and is detached from the substrate surface Wf due to the flow of diffusing the substrate surface Wf. It is preferable to set it as 1500-2500 rpm so that the carried out particle etc. can be washed away. In the following description, it is assumed that the rotation speed of the substrate W in the removing step is 2000 rpm.

  Further, the control unit 97 issues an operation command to the removing unit 45, and positions the nozzle 411 in the sky near the center of the substrate surface Wf. After the positioning of the nozzle 411 is completed, the control unit 97 issues an operation command to the removal unit 45 and opens the on-off valve 457. As a result, the removal liquid is supplied from the removal liquid supply unit 453 to the vicinity of the center of the substrate surface Wf via the pipe 455, the collective pipe 449 and the nozzle 411.

  The removal liquid supplied to the substrate surface Wf is supplied at a temperature higher than the freezing point of tertiary butanol (25.6 ° C. (degrees Celsius)) in order to quickly remove it from the substrate surface Wf by melting the tertiary butanol. It is desirable. Also, the solidified body of DIW, which is the second solidification target liquid, formed on the substrate surface Wf is quickly thawed, and unthawed ice crystals float in the liquid flowing on the substrate surface and collide with the pattern. In order to prevent damage caused by this, it is preferable to adjust the temperature to 50 ° C. (Celsius) to 90 ° C. (Celsius). In the following description, it is assumed that 80 ° C. (Celsius) DIW is supplied as the removal liquid.

  The removal liquid supplied to the vicinity of the center of the substrate surface Wf flows from the vicinity of the center of the substrate surface Wf toward the peripheral portion 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. Thereafter, it is scattered outside the substrate, collected by the drainage collecting part 21 and drained. The removal liquid diffused on the substrate surface Wf rapidly thaws the solidified body of DIW, which is the second solidification target liquid, formed on the substrate surface Wf, and removes particles and the like detached from the substrate surface Wf by the flow. In addition, the tertiary butanol in the pattern gap is dissolved and removed.

  Although the penetration speed of DIW as a removal liquid into the minute space inside the pattern gap is slow, it does not mean that it does not penetrate at all, but as the time passes, the tertiary butanol dissolves while entering the pattern gap. Tertiary butanol inside the pattern gap is replaced with DIW. Therefore, the time for carrying out the removing step may be a time sufficient to remove at least the tertiary butanol in the pattern gap.

  After the removal process is continued for a predetermined time, the control unit 97 issues an operation command to the removal unit 45 and closes the on-off valve 457. Further, the control unit 97 issues an operation command to the removing unit 45, and positions the nozzle 411 to a retracted position (a position where the nozzle 411 is out of the cup 210 in the circumferential direction).

  Next, a rinse process is performed (step S107). The control unit 97 instructs the atmosphere blocking unit 23 to move, and moves the blocking member 231 to the facing position. Further, the control unit 97 issues an operation command to the substrate holder 11 to change the rotation speed of the spin base 113 and maintain it during the rinsing process. Note that the cup 210 is maintained in the internal collection position.

  The number of rotations of the substrate W in the rinsing process is such that DIW as a rinsing liquid supplied to the substrate surface Wf and the substrate back surface Wb can diffuse over the entire surface of the substrate surface Wf and the substrate back surface Wb, and diffuses the substrate surface Wf. Therefore, it is preferable to set the pressure at 300 to 1000 rpm so that the removal liquid remaining on the substrate surface Wf can be removed. Below, the rotation speed of the board | substrate W in a rinse process is demonstrated as 800 rpm.

  After positioning the blocking member 231 at the opposing position, the control unit 97 instructs the rinsing unit 51 to operate, and opens the on-off valve 519 and the on-off valve 523.

  As a result, the rinse liquid is supplied from the rinse liquid supply unit 513 to the substrate surface Wf via the main pipe 515, the upper branch pipe 517, the upper second supply pipe 273 and the nozzle 275, and the main pipe 515 and the lower branch pipe 521. Then, the substrate is supplied to the substrate back surface Wb through the lower second supply pipe 283 and the nozzle 291. 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 in the drainage collecting part 21 and drained.

  The rinsing liquid also plays a role of removing DIW and the like scattered on the back surface Wb of the substrate W in each of the preceding steps, and particles adhering to the substrate W that have floated in the atmosphere.

  After completion of the rinsing process, the control unit 97 issues an operation command to the rinsing unit 51 and closes the on-off valve 519 and the on-off valve 523.

  Next, a drying process for drying the substrate W is performed (step S108). The control unit 97 issues an operation command to the drying gas supply unit 55, and opens the mass flow controller 559 and the mass flow controller 563 so that a predetermined flow rate is obtained. Note that the blocking member 231 of the atmosphere blocking unit 23 is maintained at the facing position, and the cup 210 is maintained at the internal collection position.

  As a result, room temperature nitrogen gas is transferred from the drying nitrogen gas supply unit 553 through the main pipe 555, the upper branch pipe 557, and the gap between the inner surface of the upper first supply pipe 271 and the outer surface of the upper second supply pipe 273. It is supplied to the front surface Wf and to the substrate back surface Wb through a gap between the inner surface of the main pipe 555, the lower branch pipe 561, and the lower first supply pipe 281 and the outer surface of the lower second supply pipe 283. Nitrogen gas fills the space between the lower surface of the blocking member 231 positioned at the opposing 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, thereby The front surface Wf and the substrate back surface Wb are prevented from coming into contact with outside air.

  After the substrate W is shut off from the outside air, the control unit 97 issues an operation command to the substrate holder 11 to change the rotation speed of the spin base 113 and maintain it during the drying process. The number of rotations of the substrate W in the drying step is preferably set to 1500 to 3000 rpm so that the rinse liquid remaining on the substrate front surface Wf and the substrate back surface Wb can be shaken out of the substrate W by centrifugal force. Below, the rotation speed of the board | substrate W in a drying process is demonstrated as 2000 rpm.

  After the drying of the substrate W is completed, the control unit 97 issues an operation command to the drying gas supply unit 55 and sets the mass flow controller 559 and the mass flow controller 563 to a flow rate of 0 (zero). Further, the control unit 97 issues an operation command to the substrate holder 11 and stops the rotation of the spin base 113. In addition, the control unit 97 issues an operation command to the atmosphere blocking unit 23 to stop the rotation of the blocking member 231. Further, the control unit 97 issues an operation command to the drainage collecting unit 21 to position the cup 210 at the home position. After the rotation of the spin base 113 stops, the control unit 97 issues an operation command to the substrate holder 11 to position the spin base 113 at a position suitable for delivery of the substrate W. Further, the control unit 97 issues an operation command to the atmosphere blocking unit 23 and moves the blocking member 231 to the separated position.

  Finally, a substrate unloading process for unloading the substrate W from the processing unit 91 is performed (step S109). After positioning the substrate holding unit 11 at a position suitable for delivery of the substrate W, the control unit 97 issues an operation command to the substrate holding unit 11 to open the substrate holding member 115 and place the substrate W on the substrate supporting unit. Put.

  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, tertiary butanol remains in a minute region inside the pattern gap and solidifies, so that it is regarded as a lump (solid matter) in which the solid butanol solidified body and the pattern are integrated. The pattern becomes thin and the pattern is structurally reinforced. Therefore, it is possible to counter the force (particularly, the force acting in parallel with the substrate surface Wf) caused by the solidification and expansion of DIW in the subsequent solidification step, and damage such as pattern peeling can be prevented.

  Moreover, when the volume change when the DIW which is the second coagulation target liquid and the tertiary butanol which is the first coagulation target liquid undergo a phase change from the liquid to the solid respectively, the tertiary butanol is smaller. Therefore, even if tertiary butanol solidifies in the pattern gap, the stress applied to the surrounding pattern is small, and damage such as pattern peeling does not occur.

In the first embodiment, tertiary butanol is used as the first coagulation target liquid, but it has a freezing point higher than that of DIW, which is the second coagulation target liquid, and the phase change from liquid to solid Other materials can be used as long as the volume change with time is smaller than DIW. For example, ethylene carbonate (ethylene carbonate) (chemical formula: C ₃ H ₄ O ₃ , freezing point: 36.4 ° C. (degrees Centigrade)). These may be diluted.

  The freezing point of the substance used as the first solidification target liquid is such that the second solidification target liquid will not evaporate after the first solidification target liquid is supplied as a liquid or when the first solidification target liquid is removed. A temperature lower than the boiling point of the second coagulation target liquid is preferable. Moreover, it is preferable that the freezing point of the substance used as the first solidification target liquid is a temperature lower than the boiling point of the removal liquid so that it can be melted and removed during the removal step.

  In the first solidification target liquid supplying step, the substrate W may be set to a temperature equal to or higher than the freezing point of the tertiary butanol so that the liquid butanol supplied to the substrate surface Wf does not solidify. For example, a method of discharging a high temperature gas to the substrate front surface Wf or the substrate back surface Wb or both surfaces, or discharging a high temperature liquid to the substrate back surface Wb can be used. Further, the temperature of the substrate W may be adjusted by discharging high temperature DIW used in the high temperature second solidification target liquid supply step onto the substrate surface Wf before the first solidification target liquid supply step.

<Second embodiment>
Next, a second embodiment of the substrate processing apparatus according to the present invention will be described. The second embodiment is greatly different from the first embodiment in that the tertiary butanol in the region other than the inside of the pattern gap is removed only by the low temperature solidification target liquid supply step without performing the high temperature second solidification target liquid supply step. As a removal step, a removal liquid having a temperature not lower than the freezing point of DIW and not higher than the freezing point of tertiary butanol is supplied.

  Since the configuration of the second embodiment is basically the same as that of the substrate processing apparatus 9 and the processing unit 91 shown in FIGS. 3 to 13, the same reference numerals are given in the following description and the description of the configuration is omitted.

  Hereinafter, operation | movement of the substrate processing apparatus 9 in 2nd embodiment is demonstrated based on FIG. FIG. 15 is a flowchart showing the overall operation of the substrate processing apparatus 9 in the second embodiment. In the second embodiment, similarly to the first embodiment, a substrate loading step (S201) for loading the substrate W into the processing unit 91 and a first solidification target liquid supplying step (S202) for supplying tertiary butanol to the substrate surface Wf. I do.

  After the first solidification target liquid has diffused over the entire surface Wf of the substrate, the control unit 997 issues an operation command to the first solidification target liquid supply unit 31 and closes the on-off valve 337. In addition, the control unit 997 issues an operation command to the first coagulation target liquid supply unit 31 to position the nozzle 311 to the retracted position of the substrate surface Wf (the position where the nozzle 311 is out of the cup 210 in the circumferential direction).

  Next, a second coagulation target liquid supply step (step S203) is performed in which DIW is supplied to the substrate surface Wf to which tertiary butanol is attached. First, the control unit 997 issues an operation command to the drainage collection unit 21 to position the cup 210 at the external collection position. The rotation of the substrate W maintains the same rotation speed as that in the first solidification target liquid supply process. Further, the blocking member 231 of the atmosphere blocking unit 23 is maintained in the separated position.

  Further, the control unit 997 issues an operation command to the second coagulation target liquid supply unit 43, and positions the nozzle 411 near the center of the substrate surface Wf. After the positioning of the nozzle 411 is completed, the control unit 997 issues an operation command to the second coagulation target liquid supply unit 43 and opens the on-off valve 437. Thus, DIW having a temperature lower than the freezing point of tertiary butanol is supplied from the second solidification target liquid supply unit 433 to the vicinity of the center of the substrate surface Wf via the pipe 439, the pipe 435, the collective pipe 449, and the nozzle 411.

  DIW coagulates tertiary butanol, shortens the time required for coagulation in the coagulation process to be described later, and because of the high temperature, DIW evaporates before the coagulation process coagulates and the DIW liquid film disappears. In order to prevent a situation in which the substrate surface Wf cannot be cleaned, the temperature is preferably adjusted to 0 ° C. to 5 ° C. (Celsius). In the following description, it is assumed that the DIW temperature is 0.5 ° C. (Celsius).

  The DIW supplied near the center of the substrate surface Wf solidifies tertiary butanol adhering to the substrate surface Wf from the center of the substrate W toward the peripheral edge of the substrate W by centrifugal force generated by the rotation of the substrate W. While flowing. Further, since tertiary butanol is easily dissolved in DIW, it is removed from the substrate surface Wf as DIW flows.

  However, the pattern formed on the substrate surface Wf is fine, and the speed at which DIW enters the minute area inside the pattern gap while dissolving tertiary butanol is such that the DIW is in the area other than the inside of the pattern gap. Much slower than the rate of dissolving and removing. Therefore, the pattern formed on the substrate surface Wf is set so that the time during which the second coagulation target liquid supplying process is performed is sufficient for the DIW to dissolve and remove the tertiary butanol at least in the region other than the inside of the pattern gap. Tertiary butanol can remain only in the gap.

  After the second coagulation target liquid supply process is continued for a predetermined time, the control unit 997 issues an operation command to the second coagulation target liquid supply unit 43 and closes the on-off valve 437. In addition, the control unit 997 issues an operation command to the second coagulation target liquid supply unit 43, and positions the nozzle 411 to a retracted position (a position where the nozzle 411 is out of the cup 210 in the circumferential direction).

  Thereafter, as in the first embodiment, a solidification step (step S204) is performed, and then a solidified body of the second solidification target liquid formed on the substrate surface Wf and a solidified butanol solidified body remaining in the pattern gap are obtained. A removal step (step S205) for removal is performed. First, the control unit 997 issues an operation command to the substrate holder 11 to change the rotation speed of the spin base 113 and maintain it during the removal process. Note that the cup 210 is maintained at the internal collection position, and the blocking member 231 of the atmosphere blocking section 23 is maintained at the separated position.

  The number of rotations of the substrate W in the removal process is such that DIW, which is the removal liquid supplied to the substrate surface Wf, can diffuse over the entire surface of the substrate surface Wf, and is detached from the substrate surface Wf due to the flow of diffusing the substrate surface Wf. It is preferable to set it as 1500-2500 rpm so that the carried out particle etc. can be washed away. In the following description, it is assumed that the rotation speed of the substrate W in the removing step is 2000 rpm.

  In addition, the control unit 997 issues an operation command to the removal unit 45, and positions the nozzle 411 in the sky near the center of the substrate surface Wf. After the positioning of the nozzle 411 is completed, the control unit 997 issues an operation command to the removal unit 45 and opens the on-off valve 457. As a result, the removal liquid is supplied from the removal liquid supply unit 453 to the vicinity of the center of the substrate surface Wf via the pipe 455, the collective pipe 449 and the nozzle 411.

  The removal liquid supplied to the substrate surface Wf is supplied at a temperature higher than the freezing point (0 ° C. (degrees Celsius)) of DIW in order to melt and remove DIW. In the following description, it is assumed that DIW at 20 ° C. (Celsius) is supplied as the removal liquid.

  The removal liquid supplied to the vicinity of the center of the substrate surface Wf flows from the vicinity of the center of the substrate surface Wf toward the peripheral portion 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. Thereafter, it is scattered outside the substrate, collected by the drainage collecting part 21 and drained. The removal liquid diffused on the substrate surface Wf thaws the DIW solidified body formed on the substrate surface Wf and pushes away particles and the like detached from the substrate surface Wf by the flow. Libutanol is also dissolved and removed.

  In this embodiment, the tertiary butanol inside the pattern gap remains solidified during the removal step, but the removal solution DIW is a good solvent for tertiary butanol (tertiary butanol is soluble in DIW). As the time elapses, the removal liquid enters the pattern gap while dissolving the tertiary butanol, and finally the tertiary butanol in the pattern gap is replaced with the removal liquid. Therefore, the time for carrying out the removing step may be a time sufficient to remove at least the tertiary butanol in the pattern gap.

  After the removal process is continued for a predetermined time, the control unit 997 issues an operation command to the removal unit 45 and closes the on-off valve 457. Further, the control unit 997 issues an operation command to the removing unit 45, and positions the nozzle 411 to a retracted position (a position where the nozzle 411 is out of the cup 210 in the circumferential direction).

  Thereafter, as in the first embodiment, a rinsing process (step S206), a drying process (step S207), and a substrate unloading process (step S208) are performed, and a series of processes is completed.

  As described above, in this embodiment, tertiary butanol remains in a minute region inside the pattern gap and solidifies, so that it is regarded as a lump (solid matter) in which the solid butanol solidified body and the pattern are integrated. The pattern becomes thin and the pattern is structurally reinforced. Therefore, it is possible to counter the force (particularly, the force acting in parallel with the substrate surface Wf) caused by the solidification and expansion of DIW in the subsequent solidification step, and damage such as pattern peeling can be prevented.

  Moreover, when the volume change when the DIW which is the second coagulation target liquid and the tertiary butanol which is the first coagulation target liquid undergo a phase change from the liquid to the solid respectively, the tertiary butanol is smaller. Therefore, even if tertiary butanol solidifies in the pattern gap, the stress applied to the surrounding pattern is small, and damage such as pattern peeling does not occur.

  In this embodiment, after supplying tertiary butanol to the substrate surface Wf in the first solidification target liquid supply step, the second solidification target liquid supply step is performed to solidify the tertiary butanol by DIW. The method of solidifying butanol is not limited to this. That is, after supplying tertiary butanol in the first solidification target liquid supplying step, it is left as it is and then cooled by the atmosphere around the substrate W or solidified by cooling with the heat of vaporization caused by vaporization of the tertiary butanol to solidify. It is also possible to do. In addition, when performing these methods, it is preferable that the freezing point of a 1st solidification object liquid is a temperature higher than normal temperature.

  It is also possible to coagulate by a method of blowing a gas having a temperature lower than the freezing point of tertiary butanol to the substrate surface Wf, a method of discharging a liquid or gas having a temperature lower than the freezing point of tertiary butanol to the substrate back surface Wb, and the like. .

In the second embodiment, tertiary butanol is used as the first solidification target liquid, but has a freezing point higher than the freezing point of the second solidification target liquid and the volume at the time of phase change from liquid to solid. Other substances can be used as long as the change is smaller than the second coagulation target liquid. For example, ethylene carbonate (ethylene carbonate) (chemical formula: C ₃ H ₄ O ₃ , freezing point: 36.4 ° C. (degrees Centigrade)). These may be diluted.

  The solidification point of the substance used as the first solidification target liquid is such that the second solidification target liquid does not evaporate after the first solidification target liquid is supplied as a liquid or when the first solidification target liquid is removed. A temperature lower than the boiling point of the second coagulation target liquid is preferable. Moreover, it is preferable that the freezing point of the substance used as the first solidification target liquid is a temperature lower than the boiling point of the removal liquid so that it can be melted and removed during the removal step.

<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 second solidification target liquid. However, the second solidification target liquid is not limited to DIW, and pure water, ultrapure water, hydrogen, etc. Even liquids such as water, carbonated water, and SC1 can be used.

  In each of the above embodiments, DIW is supplied as a removing liquid to the substrate surface Wf. However, the removing liquid is not limited to DIW, and pure water, ultrapure water, hydrogen water, carbonated water, etc. Furthermore, even liquid such as SC1 can be used.

  Further, in each of the above embodiments, the second coagulation target liquid and the removal liquid are the same DIW, but they can also be different liquids.

DESCRIPTION OF SYMBOLS 9 Substrate processing apparatus 11 Substrate holding | maintenance part 21 Drainage collection part 23 Atmosphere interruption | blocking part 31 1st coagulation object liquid supply part 35 Coagulation part 43 2nd coagulation object liquid supply part 45 Removal part 51 Rinse part 55 Gas supply part 91 for drying Processing unit 92 Fluid box 93 Indexer unit 94 Opener 95 Shuttle 96 Center robot 97 Control unit 113 Spin base 115 Substrate holding member 119 Substrate holding member driving mechanism 121 Substrate rotating mechanism 210 Cup 211 Inner component 213 Middle component 215 Outer component 217 Guard lifting mechanism 231 Blocking member 233 Support shaft 235 Blocking member rotating mechanism 241 Arm 243 Vertical shaft 245 Base member 247 Blocking member lifting mechanism 271 Upper first supply pipe 273 Upper second supply pipe 281 Lower first supply pipe 283 Lower first Two supply pipes 313 Nozzle drive Structure 331 First solidification target liquid supply unit 353 Nozzle drive mechanism 371 Solidification nitrogen gas supply unit 413 Nozzle drive mechanism 553 Drying nitrogen gas supply unit 738 Substrate holding member drive mechanism 901 Side wall 902 Upper base member 903 Lower base member 904 Processing Space 905 Upper space 906 Lower space 907 Atmosphere introduction path 908 Fan filter unit 909 Exhaust port 911 Shutter 931 Indexer robot 997 Control unit W Substrate Wb Substrate rear surface Wf Substrate surface

Claims (8)

A first solidification target liquid supply step for supplying a first solidification target liquid capable of forming a solidified body to the substrate on which the pattern is formed;
A solidified body can be formed on the substrate supplied with the first solidification target liquid, and has a freezing point lower than the freezing point of the first solidification target liquid. Supplying a second coagulation target liquid whose volume change is larger than the first coagulation target liquid, and removing the first coagulation target liquid on the substrate excluding the inside of the pattern gap;
A coagulation step in which the first coagulation target liquid and the second coagulation target liquid are cooled and solidified to a temperature below the freezing point of the second coagulation target liquid;
A substrate processing method comprising: a removing step of removing the first coagulation target liquid and the second coagulation target liquid. The substrate processing method according to claim 1,
The substrate processing method in which the first coagulation target liquid is soluble in the second coagulation target liquid. The substrate processing method according to claim 1, wherein:
The substrate processing method in which the first solidification target liquid supplying step supplies the first solidification target liquid at a temperature equal to or higher than the freezing point of the first solidification target liquid. The substrate processing method according to any one of claims 1 to 3,
The second coagulation target liquid supply step includes
After performing the high temperature second coagulation target liquid supply step of supplying the second coagulation target liquid having a temperature higher than the freezing point of the first coagulation target liquid,
A substrate processing method for performing a low-temperature second solidification target liquid supply step for supplying the second solidification target liquid having a temperature lower than that of the first solidification target liquid.   The substrate processing method according to any one of claims 1 to 4,
  The removal process is a substrate processing method in which a removal liquid is supplied to the substrate. The substrate processing method according to claim 5 ,
The substrate processing method, wherein the first coagulation target liquid is soluble in the removal liquid. The substrate processing method according to claim 5 or 6 , wherein
Said removing step, the substrate processing method of supplying the removal liquid temperature above the freezing point of the first coagulation object liquid. A substrate holder for holding the substrate on which the pattern is formed;
A first solidification target liquid supply unit that supplies a first solidification target liquid capable of forming a solidified body to the substrate;
A solidified body can be formed on the substrate supplied with the first solidification target liquid, and has a freezing point lower than the freezing point of the first solidification target liquid. A second coagulation target liquid supply unit for supplying a second coagulation target liquid whose volume change is larger than the first coagulation target liquid and removing the first coagulation target liquid on the substrate excluding the inside of the pattern gap;
A coagulation part that cools and solidifies the first coagulation target liquid and the second coagulation target liquid to a temperature below the freezing point of the second coagulation target liquid;
A substrate processing apparatus comprising: a removing unit that removes the first coagulation target liquid and the second coagulation target liquid.

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