Patent Publication Number: US-2022238327-A1

Title: Method for producing liquid containing sublimable substance, substrate drying method, and substrate processing apparatus

Description:
TECHNICAL FIELD 
     This application claims the benefit of priority to Japanese Patent Application No. 2019-100140 filed on May 29, 2019, the entire contents of the application are hereby incorporated herein by reference. 
     The present invention relates to a method to manufacture a sublimable substance-containing liquid to be removed from a substrate when drying a front surface of the substrate on which a pattern is formed. The present invention further relates to a substrate drying method and a substrate processing apparatus to dry a substrate. The substrate includes, for example, a semiconductor wafer, a substrate for a FPD (flat panel display) such as a liquid crystal display and an organic EL (electroluminescence) display, a substrate for an optical disc, a substrate for a magnetic disk, a substrate for a magneto-optical disc, a substrate for a photomask, a ceramic substrate, a substrate for a solar cell, and the like. 
     BACKGROUND ART 
     In a manufacturing process for semiconductor devices or FPDs, required processes are conducted to a substrate such as a semiconductor wafer or a glass substrate for a FPD. Such processes include supplying a substrate with a processing liquid such as a chemical liquid or a rinse liquid. After the processing liquid is supplied, the processing liquid is removed from the substrate to dry the substrate. 
     In a case where a pattern is formed on a front surface of the substrate, when the substrate is being dried, a force due to the surface tension of the processing liquid adhering to the substrate applies to the pattern, so that the pattern may collapse. As countermeasures against this, a liquid having a lower surface tension such as IPA (isopropyl alcohol) is supplied to the substrate, or a hydrophobizing agent is supplied to the substrate in order to bring the contact angle of the liquid to the pattern closer to  90  degrees. However, a collapsing force to collapse the pattern does not become zero even when using IPA or the hydrophobizing agent, so that these countermeasures may not sufficiently prevent the collapse of the pattern depending on the strength of the pattern. 
     Recently, attention is focused on sublimation drying as a technique to prevent the collapse of the pattern. For example, Patent Literature 1 discloses a substrate drying method and a substrate processing apparatus to conduct the sublimation drying. Patent Literature 1 discloses dissolving an ammonium fluorosilicate as a sublimable substance (solute) in a pure water (DIW) or a mixed liquid of a DIW and an IPA (isopropyl alcohol), and dissolving a camphor or a naphthalene as the sublimable substance (solute) in an alcohol such as IPA. 
     Patent Literature 1 also discloses supplying a solution of the sublimable substance to the substrate after the pattern is formed on a SiN film, and supplying the solution of the sublimable substance to the substrate after the pattern is formed on a photoresist film. After the solution of the sublimable substance is supplied to the substrate, a film consisting of a solid sublimable substance is formed. After that, the substrate is transferred to a hot plate unit from a liquid processing unit. The substrate is heated by the hot plate unit at a temperature higher than a sublimation temperature of the sublimable substance. Thus, the sublimable substance sublimates and is removed from the substrate. 
     CITATION LIST 
     Patent Literature 
     Patent Literature 1: JP 2018-139331 A 
     SUMMARY OF INVENTION 
     Technical Problem 
     According to the research by the present inventors, it was found that it is also important to consider the affinity between the solvent and the pattern in order to reduce the collapse rate of pattern in the sublimation drying. 
     Specifically, when the affinity of the solvent with respect to the surface of the pattern is high, the solvent is likely to be held by the surface of the pattern. Thus, a lot of the solvent may remain between the patterns even after forming a solidified film including the sublimable substance. For example, when the surface of the pattern is hydrophilic and the hydrophilicity of the solvent is high, it is considered that a lot of the solvent remains between the patterns even after the solidified film is formed. In this case, it is considered that the solidified film is formed above the pattern while an area between the patterns is filled with a liquid containing the solvent (see  FIG. 8B ). 
     When the liquid containing the solvent remains between the patterns after forming the solidified film, a force due to the surface tension of the solvent is applied to the pattern. When the strength of the pattern is low, the pattern collapses even with such a force. Thus, the solvent is also required to have a low affinity with respect to the surface of the pattern. In Patent Literature 1, such a point is not taken into consideration at all. That is, the present inventors have found a new problem that the collapse rate of the pattern cannot be sufficiently reduced when the sublimable substance-containing liquid contains a solvent having an inappropriate affinity with respect to the pattern. 
     Thus, an object of the present invention is to provide a manufacturing method for a sublimable substance-containing liquid that is able to manufacture the sublimable substance-containing liquid containing a solvent having an appropriate affinity with respect to a pattern. Another object of the present invention is to provide a substrate drying method and a substrate processing apparatus that are able to dry a substrate using such a sublimable substance-containing liquid. 
     Solution to Problem 
     A preferred embodiment of the present invention provides a manufacturing method for a sublimable substance-containing liquid to be removed from a substrate when drying a front surface of the substrate on which a pattern is formed, the manufacturing method for the sublimable substance-containing liquid including a sublimable substance selecting step of selecting a sublimable substance based on whether a surface of the pattern is hydrophilic or hydrophobic, a solvent selecting step of selecting a solvent for hydrophilicity having less solubility in water than that of the sublimable substance selected in the sublimable substance selecting step in a case in which the surface of the pattern is hydrophilic and selecting a solvent for hydrophobicity having less solubility in oil than that of the sublimable substance selected in the sublimable substance selecting step in a case in which the surface of the pattern is hydrophobic, and a dissolving step of dissolving the sublimable substance selected in the sublimable substance selecting step in the solvent selected in the solvent selecting step. 
     In this method, the sublimable substance-containing liquid containing the sublimable substance and the solvent is manufactured. The sublimable substance-containing liquid is supplied to the front surface of the substrate on which the pattern is formed and then removed from the substrate. Thus, the substrate is dried. When removing the sublimable substance-containing liquid from the substrate, the solvent is evaporated from the sublimable substance-containing liquid on the front surface of the substrate, for example. Thus, the solidified film including the sublimable substance is formed on the front surface of the substrate. After that, the solidified film is sublimated and removed from the front surface of the substrate. Thus, the sublimable substance-containing liquid is removed. 
     In a case where the surface of the pattern is hydrophilic, the solvent having less solubility in water than that of the sublimable substance is contained in the sublimable substance-containing liquid. When the surface of the pattern is hydrophilic and the hydrophilicity of the solvent is high, the solvent is likely to be held on the surface of the pattern, so that a lot of the solvent remains between the patterns even after forming the solidified film. In this case, the collapsing force to collapse the pattern is applied to the pattern from the solvent. It is possible to reduce the solvent remaining between the patterns after forming the solidified film to zero or a value close to it by using the solvent having low hydrophilicity. 
     In a case where the surface of the pattern is hydrophobic, the solvent having less solubility in oil than that of the sublimable substance is contained in the sublimable substance-containing liquid. When the surface of the pattern is hydrophobic and the hydrophobicity of the solvent is high, the solvent is likely to be held on the surface of the pattern, so that a lot of the solvent remains between the patterns even after forming the solidified film. In this case, the collapsing force to collapse the pattern is applied to the pattern from the solvent. It is possible to reduce the solvent remaining between the patterns after forming the solidified film to zero or a value close to it by using the solvent having low hydrophobicity. 
     In this way, the solvent contained in the sublimable substance-containing liquid has less affinity with respect to the surface of the pattern than the sublimable substance contained in the sublimable substance-containing liquid regardless of whether the surface of the pattern is hydrophilic or hydrophobic. Thus, it is possible to reduce the solvent remaining between the patterns after forming the solidified film and to weaken the collapsing force applied to the pattern during and after the solidified film is formed. Accordingly, it is possible to manufacture the sublimable substance-containing liquid to dry the substrate with the low collapse rate of the pattern regardless of whether the surface of the pattern is hydrophilic or hydrophobic. 
     In the preferred embodiment, at least one of the following features may be added to the manufacturing method for the sublimable substance-containing liquid. 
     The manufacturing method for the sublimable substance-containing liquid further includes a property determining step of regarding the surface of the pattern as hydrophilic before selecting the sublimable substance and the solvent when a hydrophilic portion and a hydrophobic portion are included in the surface of the pattern and an upper end portion of a side surface of the pattern is hydrophilic and regarding the surface of the pattern as hydrophobic before selecting the sublimable substance and the solvent when the hydrophilic portion and the hydrophobic portion are included in the surface of the pattern and the upper end portion of the side surface of the pattern is hydrophobic. 
     In this method, in a case where the hydrophilic portion and the hydrophobic portion are included in the surface of the pattern, if the upper end portion of the side surface of the pattern is hydrophilic, the surface of the pattern is regarded as hydrophilic. In a case where the hydrophilic portion and the hydrophobic portion are included in the surface of the pattern, if the upper end portion of the side surface of the pattern is hydrophobic, the surface of the pattern is regarded as hydrophobic. That is, it is determined whether the surface of the pattern is hydrophilic or hydrophobic based on the property of the upper end portion of the side surface of the pattern. 
     When a liquid surface (interface between gas and liquid) is formed between two adjacent projecting patterns, the collapsing force due to the surface tension is applied to the patterns. This collapsing force increases as a distance from the root of the pattern to the liquid surface increases. Thus, even when the liquid surface is formed between the two adjacent projecting patterns, if the distance from the root (lower end) of the pattern to the liquid surface is short, the collapsing force applied to the pattern is weak. 
     If the surface of the pattern is regarded as hydrophobic when the hydrophilic portion and the hydrophobic portion are included in the surface of the pattern and the upper end portion of the side surface of the pattern is hydrophilic, it is likely that the liquid surface of the solvent is formed at the upper end portion of the side surface of the pattern after forming the solidified film and the large collapsing force is applied to the pattern. If the surface of the pattern is regarded as hydrophilic, even when the liquid surface of the solvent is formed between the patterns, the liquid surface of the solvent is disposed on the root side of the pattern. Thus, it is possible to shorten the distance from the root of the pattern to the liquid surface. 
     For the same reason, if the surface of the pattern is regarded as hydrophobic when the hydrophilic portion and the hydrophobic portion are included in the surface of the pattern and the upper end portion of the side surface of the pattern is hydrophobic, even when the liquid surface of the solvent is formed between the patterns, it is possible to shorten the distance from the root of the pattern to the liquid surface. Thus, it is possible to manufacture the sublimable substance-containing liquid to weaken the collapsing force applied to the pattern and to lower the collapse rate of the pattern. 
     Another preferred embodiment of the present invention provides a substrate drying method including a sublimable substance-containing liquid supplying step of supplying a front surface of a substrate with a sublimable substance-containing liquid manufactured by the manufacturing method for the sublimable substance-containing liquid, a solidified film forming step of forming a solidified film including the sublimable substance onto the front surface of the substrate by evaporating the solvent from the sublimable substance-containing liquid on the front surface of the substrate, and a sublimating step of removing the solidified film from the front surface of the substrate by sublimating the solidified film. 
     In this method, the sublimable substance-containing liquid containing the sublimable substance, which corresponds to the solute, and the solvent is supplied to the front surface of the substrate on which the pattern is formed. After that, the solvent is evaporated from the sublimable substance-containing liquid. Thus, the solidified film including the sublimable substance is formed on the front surface of the substrate. After that, the solidified film on the substrate is changed to gas without passing through to a liquid. Thus, the solidified film is removed from the front surface of the substrate. Accordingly, it is possible to lower the collapse rate of the patterns as compared to the conventional drying method such as spin drying. 
     Still another preferred embodiment of the present invention provides a substrate processing method to dry a front surface of a substrate on which a pattern is formed, the substrate processing method including a sublimable substance selecting step of selecting a sublimable substance based on whether a surface of the pattern is hydrophilic or hydrophobic, a solvent selecting step of selecting a solvent for hydrophilicity having less solubility in water than that of the sublimable substance selected in the sublimable substance selecting step in a case in which the surface of the pattern is hydrophilic and selecting a solvent for hydrophobicity having less solubility in oil than that of the sublimable substance selected in the sublimable substance selecting step in a case in which the surface of the pattern is hydrophobic, a dissolving step of manufacturing a sublimable substance-containing liquid containing the sublimable substance and the solvent by dissolving the sublimable substance selected in the sublimable substance selecting step in the solvent selected in the solvent selecting step, a sublimable substance-containing liquid supplying of supplying the sublimable substance-containing liquid manufactured in the dissolving step to the front surface of the substrate, a solidified film forming step of forming a solidified film including the sublimable substance onto the front surface of the substrate by evaporating the solvent from the sublimable substance-containing liquid on the front surface of the substrate, and a sublimating step of removing the solidified film from the front surface of the substrate by sublimating the solidified film. 
     In this method, the sublimable substance-containing liquid containing the sublimable substance, which corresponds to the solute, and the solvent is manufactured and the manufactured sublimable substance-containing liquid is supplied to the front surface of the substrate on which the pattern. After that, the solvent is evaporated from the sublimable substance-containing liquid. Thus, the solidified film including the sublimable substance is formed on the front surface of the substrate. After that, the solidified film on the substrate is changed to gas without passing through to a liquid. Thus, the solidified film is removed from the front surface of the substrate. Thus, it is possible to lower the collapse rate of the pattern as compared to the conventional drying method such as spin drying. 
     In a case where the surface of the pattern is hydrophilic, the solvent having less solubility in water than that of the sublimable substance is contained in the sublimable substance-containing liquid. When the surface of the pattern is hydrophilic and the hydrophilicity of the solvent is high, the solvent is likely to be held on the surface of the pattern, so that a lot of the solvent remains between the patterns even after forming the solidified film. In this case, the collapsing force to collapse the pattern is applied to the pattern from the solvent. It is possible to reduce the solvent remaining between the patterns after forming the solidified film to zero or a value close to it by using the solvent having low hydrophilicity. 
     In a case where the surface of the pattern is hydrophobic, the solvent having less solubility in oil than that of the sublimable substance is contained in the sublimable substance-containing liquid. When the surface of the pattern is hydrophobic and the hydrophobicity of the solvent is high, the solvent is likely to be held on the surface of the pattern, so that a lot of the solvent remains between the patterns even after forming the solidified film. In this case, the collapsing force to collapse the pattern is applied to the pattern from the solvent. It is possible to reduce the solvent remaining between the patterns after forming the solidified film to zero or a value close to it by using the solvent having low hydrophobicity. 
     In this way, the solvent contained in the sublimable substance-containing liquid has less affinity with respect to the surface of the pattern than the sublimable substance contained in the sublimable substance-containing liquid regardless of whether the surface of the pattern is hydrophilic or hydrophobic. Thus, it is possible to reduce the solvent remaining between the patterns after forming the solidified film and to weaken the collapsing force applied to the pattern during and after the solidified film is formed. Accordingly, it is possible to dry the substrate with the low collapse rate of the pattern regardless of whether the surface of the pattern is hydrophilic or hydrophobic. 
     In the preferred embodiment, at least one of the following features may be added to the substrate drying method. 
     The substrate drying method further includes a property determining step of regarding the surface of the pattern as hydrophilic before selecting the sublimable substance and the solvent when a hydrophilic portion and a hydrophobic portion are included in the surface of the pattern and an upper end portion of a side surface of the pattern is hydrophilic and regarding the surface of the pattern as hydrophobic before selecting the sublimable substance and the solvent when the hydrophilic portion and the hydrophobic portion are included in the surface of the pattern and the upper end portion of the side surface of the pattern is hydrophobic. 
     In this method, in a case where the hydrophilic portion and the hydrophobic portion are included in the surface of the pattern, if the upper end portion of the side surface of the pattern is hydrophilic, the surface of the pattern is regarded as hydrophilic. In a case where the hydrophilic portion and the hydrophobic portion are included in the surface of the pattern, if the upper end portion of the side surface of the pattern is hydrophobic, the surface of the pattern is regarded as hydrophobic. That is, it is determined whether the surface of the pattern is hydrophilic or hydrophobic based on the property of the upper end portion of the side surface of the pattern. 
     When a liquid surface (interface between gas and liquid) is formed between two adjacent projecting patterns, the collapsing force due to the surface tension is applied to the patterns. This collapsing force increases as a distance from the root of the pattern to the liquid surface increases. Thus, even when the liquid surface is formed between the two adjacent projecting patterns, if the distance from the root (lower end) of the pattern to the liquid surface is short, the collapsing force applied to the pattern is weak. 
     If the surface of the pattern is regarded as hydrophobic when the hydrophilic portion and the hydrophobic portion are included in the surface of the pattern and the upper end portion of the side surface of the pattern is hydrophilic, it is likely that the liquid surface of the solvent is formed at the upper end portion of the side surface of the pattern after forming the solidified film and the large collapsing force is applied to the pattern. If the surface of the pattern is regarded as hydrophilic, even when the liquid surface of the solvent is formed between the patterns, the liquid surface of the solvent is disposed on the root side of the pattern. Thus, it is possible to shorten the distance from the root of the pattern to the liquid surface. 
     For the same reason, if the surface of the pattern is regarded as hydrophobic when the hydrophilic portion and the hydrophobic portion are included in the surface of the pattern and the upper end portion of the side surface of the pattern is hydrophobic, even when the liquid surface of the solvent is formed between the patterns, it is possible to shorten the distance from the root of the pattern to the liquid surface. Thus, it is possible to weaken the collapsing force applied to the pattern and to lower the collapse rate of the pattern. 
     Still another preferred embodiment of the present invention provides a substrate processing apparatus to dry a front surface of a substrate on which a pattern is formed, the substrate processing apparatus including a sublimable substance selecting unit that selects a sublimable substance based on whether a surface of the pattern is hydrophilic or hydrophobic, a solvent selecting unit that selects a solvent for hydrophilicity having less solubility in water than that of the sublimable substance selected by the sublimable substance selecting unit in a case in which the surface of the pattern is hydrophilic and selects a solvent for hydrophobicity having less solubility in oil than that of the sublimable substance selected by the sublimable substance selecting unit in a case in which the surface of the pattern is hydrophobic, a dissolving unit that manufactures a sublimable substance-containing liquid containing the sublimable substance and the solvent by dissolving the sublimable substance selected by the sublimable substance selecting unit in the solvent selected by the solvent selecting unit, a sublimable substance-containing liquid supplying unit that supplies the sublimable substance-containing liquid manufactured by the dissolving unit to the front surface of the substrate, a solidified film forming unit that forms a solidified film including the sublimable substance onto the front surface of the substrate by evaporating the solvent from the sublimable substance-containing liquid on the front surface of the substrate, and a sublimating unit that removes the solidified film from the front surface of the substrate by sublimating the solidified film. According to this arrangement, the same effects as those of the substrate drying method described above can be obtained. 
     Whether the surface of the pattern is hydrophilic or hydrophobic may be determined based on the property of the surface of the pattern (hydrophilicity or hydrophobicity) when the sublimable substance-containing liquid first comes into contact with the front surface of the substrate. For example, when a chemical liquid is supplied to the front surface of the substrate before supplying the sublimable substance-containing liquid, the surface of the pattern may change from one of hydrophilicity and hydrophobicity to the other of hydrophilicity and hydrophobicity. In such a case, the sublimable substance and the solvent may be selected based on the surface property of the pattern after supplying the chemical liquid. 
     In a case where the selected sublimable substance is insoluble or difficult to dissolve in the selected solvent, the dissolving step may include an amphiphilic molecule adding step of dissolving the selected sublimable substance in the selected solvent by mixing the selected sublimable substance, the selected solvent, and an amphiphilic molecule including both of a hydrophilic group and a hydrophobic group. The dissolving unit may include an amphiphilic molecule adding unit that dissolves the selected sublimable substance in the selected solvent by mixing the selected sublimable substance, the selected solvent, and an amphiphilic molecule including both of a hydrophilic group and a hydrophobic group. In these cases, the solvent dissolves in the amphiphilic molecule and the sublimable substance dissolves in the mixed liquid of the solvent and the amphiphilic molecule. Thus, even if the sublimable substance is insoluble or difficult to dissolve in the solvent, it is possible to manufacture the sublimable substance-containing liquid containing the sublimable substance and the solvent. 
     The sublimable substance selecting step may be a step of selecting the sublimable substance including a hydrophilic group in a case where the surface of the pattern is hydrophilic and selecting the sublimable substance including a hydrophobic group in a case where the surface of the pattern is hydrophobic. The sublimable substance selecting unit may be a unit that selects the sublimable substance including a hydrophilic group in a case where the surface of the pattern is hydrophilic and selects the sublimable substance including a hydrophobic group in a case where the surface of the pattern is hydrophobic. In these cases, it is possible to manufacture the sublimable substance-containing liquid containing the sublimable substance having high affinity with respect to the surface of the pattern. Thus, it is possible to further reduce the solvent remaining between the patterns after forming the solidified film. 
     The above and other objects, features, and advantages of the present invention will become more apparent from the following detailed description of the preferred embodiments with reference to the attached drawings. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
       [ FIG. 1A ] a schematic view of a substrate processing apparatus according to a first preferred embodiment of the present invention when viewed from above. 
       [ FIG. 1B ] a schematic view of the substrate processing apparatus when viewed from the side. 
       [ FIG. 2 ] a schematic view of the inside of a processing unit, when viewed horizontally, which is provided in the substrate processing apparatus. 
       [ FIG. 3 ] a schematic view showing a sublimable substance-containing liquid supplying unit provided in the substrate processing apparatus. 
       [ FIG. 4 ] cross-sectional views showing examples of a cross-section of the substrate to be processed by the substrate processing apparatus. 
       [ FIG. 5 ] a block diagram showing a hardware of a controller. 
       [ FIG. 6 ] a process chart for describing an example of a processing of a substrate which is executed by the substrate processing apparatus. 
       [ FIG. 7A ] a schematic view for describing phenomena that are expected to occur in the processing of the substrate shown in  FIG. 6  during the period of time from supplying an upper surface of the substrate with the sublimable substance-containing liquid to removing the solidified film from the upper surface of the substrate. 
       [ FIG. 76 ] a schematic view for describing the phenomena. 
       [ FIG. 7C ] a schematic view for describing the phenomena. 
       [ FIG. 7D ] a schematic view for describing the phenomena. 
       [ FIG. 7E ] a schematic view for describing the phenomena. 
       [ FIG. 7F ] a schematic view for describing the phenomena. 
       [ FIG. 8A ] a schematic view for describing phenomena that are expected to occur in the processing of the substrate shown in  FIG. 6  during the period of time from supplying the upper surface of the substrate with the sublimable substance-containing liquid to removing the solidified film from the upper surface of the substrate. 
       [ FIG. 8B ] a schematic view for describing the phenomena. 
       [ FIG. 8C ] a schematic view for describing the phenomena. 
       [ FIG. 8D ] a schematic view for describing the phenomena. 
       [ FIG. 9 ] a schematic view showing a sublimable substance-containing liquid supplying unit provided in a substrate processing apparatus according to a second preferred embodiment of the present invention. 
       [ FIG. 10 ] a process chart for describing another example of the sublimable substance-containing liquid supplying step shown in  FIG. 6 . 
     
    
    
     DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS 
     In the description below, unless otherwise specified, it is to be understood that the atmospheric pressure inside a substrate processing apparatus  1  is kept at atmospheric pressure inside a clean room in which the substrate processing apparatus  1  is installed (e.g., one atmospheric pressure or a value in its vicinity). 
       FIG. 1A  is a schematic view of a substrate processing apparatus  1  according to a first preferred embodiment of the present invention when viewed from above.  FIG. 18  is a schematic view of the substrate processing apparatus  1  when viewed from the side. 
     As shown in  FIG. 1A , the substrate processing apparatus  1  is a single substrate processing-type apparatus that processes disc-shaped substrates W such as a semiconductor wafer one by one. The substrate processing apparatus  1  includes load ports LP that hold carriers CA that house one or more substrates W, a plurality of processing units  2  that process the substrates W transferred from the carriers CA on the load ports LP with a processing fluid such as a processing liquid or a processing gas, transfer robots that transfer the substrates W between the carriers CA on the load ports LP and the processing units  2  and a controller  3  that controls the substrate processing apparatus  1 . 
     The transfer robots include an indexer robot IR that carries the substrates W into and out from the carriers CA on the load ports LP and a center robot CR that carries the substrates W into and out from the processing units  2 . The indexer robot IR transfers the substrates W between the load ports LP and the center robot CR, the center robot CR transfers the substrates W between the indexer robot IR and the processing units  2 . The center robot CR includes hands H 1  that support the substrates W and the indexer robot IR includes hands H 2  that support the substrates W. 
     The plurality of processing units  2  form a plurality of towers TW disposed around the center robot CR in a plan view.  FIG. 1A  shows an example in which four towers TW are formed. The center robot CR is able to access each of the towers TW. As shown in  FIG. 1B , each of the towers TW includes the plurality of (for example, three) processing units  2  that are stacked vertically. 
     As shown in  FIG. 1A , the substrate processing apparatus  1  includes a plurality of (for example, four) fluid boxes  4  that house fluid devices such as valve. The four fluid boxes  4  correspond to the four towers TW, respectively. Liquid in a cabinet CC is supplied through any of the fluid boxes FB to all the processing units  2  included in the tower TW corresponding to this fluid box FB. The cabinet CC of the substrate processing apparatus  1  may be disposed around an outer wall la of the substrate processing apparatus  1  or may be disposed in the basement of a clean room in which the substrate processing apparatus  1  is installed. 
       FIG. 2  is a schematic view of the inside of a processing unit  2 , when viewed horizontally, which is provided in the substrate processing apparatus  1 . 
     The processing unit  2  is a wet-processing unit  2 W that provides the processing liquid to the substrate W. The processing unit  2  includes a box-shaped chamber  4  that has an internal space, a spin chuck  10  that rotates one substrate W around a vertical rotation axis A 1  passing through the central portion of the substrate W while holding the substrate W horizontally within the chamber  4  and a tubular processing cup  21  that surrounds the spin chuck  10  around the rotation axis A 1 . 
     The chamber  4  includes a box-shaped partition wall  5  provided with a carry-in/carry-out port  5   b  through which the substrate W passes, and a shutter  7  to open and close the carry-in/carry-out port  5   b . An FFU  6  (fan filter unit) is disposed on an air outlet  5   a  that is provided in the upper portion of the partition wall  5 . The FFU  6  supplies clean air (filtered air) all the time through the air outlet  5   a  into the chamber  4 . A gas inside the chamber  4  is discharged from the chamber  4  through an exhaust duct  8  that is connected to the bottom portion of the processing cup  21 . Thus, the downflow of clean air is formed inside the chamber  4  all the time. The flow rate of the discharged gas that is discharged into the exhaust duct  8  changes depending on the opening degree of an exhaust valve  9  that is disposed inside the exhaust duct  8 . 
     The spin chuck  10  includes a disc-shaped spin base  12  that is held in a horizontal posture, a plurality of chuck pins  11  that hold the substrate W in the horizontal posture above the spin base  12 , a spin shaft  13  that extends downward from the central portion of the spin base  12  and a spin motor  14  that rotates the spin base  12  and the chuck pins  11  by rotating the spin shaft  13 . The spin chuck  10  is not limited to a clamping type chuck that brings the chuck pins  11  into contact with the outer circumferential surface of the substrate W, and the spin chuck  10  may be a vacuum-type chuck that sucks the rear surface (lower surface) of the substrate W that is a non-device formation surface to the upper surface  12   u  of the spin base  12  so as to hold the substrate W horizontally. 
     The processing cup  21  includes a plurality of guards  24  to receive a processing liquid discharged outwardly from the substrate W, a plurality of cups  23  to receive the processing liquid guided downwardly by the plurality of guards  24 , and a cylindrical outer wall member  22  that surrounds the plurality of guards  24  and the plurality of cups  23 .  FIG. 2  shows an example in which four guards  24  and three cups  23  are provided, and the outermost cup  23  is integral with the guard  24  that is the third from the top. 
     The guard  24  includes a cylindrical portion  25  that surrounds the spin chuck  10 , and an annular ceiling portion  26  that extends diagonally upwardly toward the rotation axis A 1  from the upper end portion of the cylindrical portion  25 . The plurality of ceiling portions  26  are stacked in the vertical direction, and the plurality of cylindrical portions  25  are disposed concentrically. The annular upper end of the ceiling portions  26  corresponds to the upper end  24   u  of the guards  24  that surround the substrate W and the spin base  12  in a plan view. The plurality of cups  23  are disposed below the plurality of cylindrical portions  25 , respectively. The cup  23  defines an annular liquid-receiving groove that receives a processing liquid guided downwardly by the guard  24 . 
     The processing unit  2  includes a guard elevating/lowering unit  27  to individually elevate and lower the plurality of guards  24 . The guard elevating/lowering unit  27  locates the guards  24  at an arbitrary position within a range from an upper position to a lower position.  FIG. 2  shows a state in which two guards  24  are disposed at an upper position, and the remaining two guards  24  are disposed at a lower position. The upper position is a position in which the upper end  24 u of the guards  24  is disposed higher than a holding position in which the substrate W held by the spin chuck  10  is disposed. The lower position is a position in which the upper end  24 u of the guards  24  is disposed lower than the holding position. 
     A processing liquid is supplied to the rotating substrate W in a state in which at least one guard  24  is disposed at the upper position. When the processing liquid is supplied to the substrate W in the state, the processing liquid flies off outward from the substrate W. The flied-off processing liquid collides with the inner surface of the guard  24  horizontally opposing the substrate W, and is then guided with the cup  23  that is associated with the guard  24 . This allows the processing liquid discharged from the substrate W to be collected in the cup  23 . 
     The processing unit  2  includes a plurality of nozzles to discharge the processing liquid to the substrate W held by the spin chuck  10 . The plurality of nozzles include a chemical liquid nozzle  31  to discharge a chemical liquid to the upper surface of the substrate W, a rinse liquid nozzle  35  to discharge a rinse liquid to the upper surface of the substrate W, a sublimable substance-containing liquid nozzle  39  to discharge a sublimable substance-containing liquid to the upper surface of the substrate W, and a replacing liquid nozzle  43  to discharge a replacing liquid to the upper surface of the substrate W. 
     The chemical liquid nozzle  31  may be a scan nozzle that is horizontally movable within the chamber  4  or alternatively, may be a fixed nozzle that is secured with respect to the partition wall  5  of the chamber  4 . The same applies to the rinse liquid nozzle  35 , the sublimable substance-containing liquid nozzle  39 , and the replacing liquid nozzle  43 .  FIG. 2  shows an example in which each of the chemical liquid nozzle  31 , the rinse liquid nozzle  35 , the sublimable substance-containing liquid nozzle  39 , and the replacing liquid nozzle  43  is a scan nozzle, and four nozzle moving units associated with those four nozzles respectively are provided. 
     The chemical liquid nozzle  31  is connected to a chemical liquid piping  32  that guides a chemical liquid to the chemical liquid nozzle  31 . When a chemical liquid valve  33  interposed in the chemical liquid piping  32  is opened, the chemical liquid is continuously discharged downwardly from the discharge port of the chemical liquid nozzle  31 . The chemical liquid to be discharged from the chemical liquid nozzle  31  may be a liquid that contains at least one of sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid, phosphorus acid, acetic acid, ammonia water, a hydrogen peroxide solution, organic acid (e.g., such as citric acid or oxalic acid), organic alkaline (e.g., TMAH: tetramethyl ammonium hydroxide), a surface-active agent, and a corrosion inhibitor, or alternatively, may be a solution other than those. 
     A 1 though not shown, the chemical liquid valve  33  includes a valve body provided with an annular valve seat through which the chemical liquid passes, a valve member which is movable with respect to the valve seat and an actuator which moves the valve member between a closed position where the valve member is in contact with the valve seat and an open position where the valve member is separated from the valve seat. The same applies to other valves. The actuator may be a pneumatic actuator or an electric actuator or an actuator other than those. The controller  3  opens and closes the chemical liquid valve  33  by controlling the actuator. 
     The chemical liquid nozzle  31  is connected to a nozzle moving unit  34  that moves the chemical liquid nozzle  31  at least in one of the vertical and horizontal directions. The nozzle moving unit  34  horizontally moves the chemical liquid nozzle  31  between a processing position at which the chemical liquid discharged from the chemical liquid nozzle  31  is supplied to the upper surface of the substrate W and a standby position at which the chemical liquid nozzle  31  is positioned around the processing cup  21  in a plan view. 
     The rinse liquid nozzle  35  is connected to a rinse liquid piping  36  that guides a rinse liquid to the rinse liquid nozzle  35 . When a rinse liquid valve  37  interposed in the rinse liquid piping  36  is opened, the rinse liquid is continuously discharged downwardly from the discharge port of the rinse liquid nozzle  35 . For example, the rinse liquid discharged from the rinse liquid nozzle  35  is pure water (DIW (Deionized Water)). The rinse liquid may be any one of carbonated water, electrolyzed ion water, hydrogen water, ozone water, and hydrochloric acid water of a diluted concentration (e.g., approximately 10 to 100 ppm). 
     The rinse liquid nozzle  35  is connected to a nozzle moving unit  38  that moves the rinse liquid nozzle  35  at least in one of the vertical and horizontal directions. The nozzle moving unit  38  horizontally moves the rinse liquid nozzle  35  between the processing position, at which the rinse liquid discharged from the rinse liquid nozzle  35  is supplied to the upper surface of the substrate W, and the standby position at which the rinse liquid nozzle  35  is located around the processing cup  21  in a plan view. 
     The sublimable substance-containing liquid nozzle  39  is connected to a sublimable substance-containing liquid piping  40  that guides the processing liquid to the sublimable substance-containing liquid nozzle  39 . When a sublimable substance-containing liquid valve  41  interposed in the sublimable substance-containing liquid piping  40  is opened, the sublimable substance-containing liquidis continuously discharged downwardly from the discharge port of the sublimable substance-containing liquid nozzle  39 . Similarly, the replacing liquid nozzle  43  is connected to a replacing liquid piping  44  that guides a replacing liquid to the replacing liquid nozzle  43 . When a replacing liquid valve  45  interposed in the replacing liquid piping  44  is opened, the replacing liquid is continuously discharged downwardly from the discharge port of the replacing liquid nozzle  43 . 
     The sublimable substance-containing liquid is a solution that contains a sublimable substance corresponding to a solute, and a solvent in which the sublimable substance dissolves. The sublimable substance-containing liquid may further contain a substance other than the sublimable substance and the solvent. The sublimable substance may be a substance that changes from solid to gas without passing through to a liquid at normal temperature (the same as the room temperature) or at normal pressure (the pressure inside the substrate processing apparatus  1 , e.g., at one atmospheric pressure or a value in its vicinity). 
     The freezing point of the sublimable substance-containing liquid (the freezing point at one atmospheric pressure; the same applies hereinafter) is lower than the room temperature (23° C. or a value in its vicinity). The substrate processing apparatus  1  is disposed inside a clean room that is maintained at the room temperature. Therefore, even without heating the sublimable substance-containing liquid, the sublimable substance-containing liquid can be maintained in the form of liquid. The freezing point of the sublimable substance is higher than the freezing point of the sublimable substance-containing liquid. The freezing point of the sublimable substance is higher than the room temperature. The sublimable substance is solid at the room temperature. The freezing point of the sublimable substance may be higher than the boiling point of the solvent. The vapor pressure of the solvent is higher than the vapor pressure of the sublimable substance. 
     For example, the sublimable substance may be any one of alcohol (for example, 2-methyl-2-propanol (alias: tert-butyl alcohol, t-butyl alcohol, tertiary butyl alcohol) or cyclohexanol), a fluorinated hydrocarbon compound, 1,3,5-trioxane (alias: metaformaldehyde), camphor, naphthalene and iodine, or alternatively, may be a substance other than those. 
     For example, the solvent may be at least one type selected from the group consisting of pure water, IPA, methanol, HFE (hydrofluoroether), acetone, PGMEA (propylene glycol monomethyl ether acetate), PGEE (propylene glycol monoethyl ether, 1-ethoxy-2-propanol), and ethylene glycol. IPA has a higher vapor pressure than water and a lower surface tension than water. 
     As described below, the replacing liquid is supplied to the upper surface of the substrate W covered with the liquid film of the rinse liquid, and the sublimable substance-containing liquid is supplied to the upper surface of the substrate W covered with the liquid film of the replacing liquid. The replacing liquid may be any liquid as long as the replacing liquid dissolves in both the rinse liquid and the sublimable substance-containing liquid. The replacing liquid is IPA (liquid), for example. The replacing liquid may be a liquid mixture of IPA and HFE, or may be a liquid other than these. 
     When the replacing liquid is supplied to the upper surface of the substrate W covered with the liquid film of rinse liquid, most of the rinse liquid on the substrate W is washed away by the replacing liquid and thus discharged from the substrate W. The small amount of remaining rinse liquid is dissolved in the replacing liquid to be diffused into the replacing liquid. The diffused rinse liquid is discharged from the substrate W together with the replacing liquid. Therefore, the rinse liquid on the substrate W can be efficiently replaced with the replacing liquid. For the same reason, the replacing liquid on the substrate W can be efficiently replaced with the sublimable substance-containing liquid. This makes it possible to reduce the rinse liquid contained in the sublimable substance-containing liquid on the substrate W. 
     The sublimable substance-containing liquid nozzle  39  is connected to a nozzle moving unit  42  that moves the sublimable substance-containing liquid nozzle  39  at least in one of the vertical and horizontal directions. The nozzle moving unit  42  horizontally moves the sublimable substance-containing liquid nozzle  39  between the processing position, at which the sublimable substance-containing liquid discharged from the sublimable substance-containing liquid nozzle  39  is supplied to the upper surface of the substrate W, and the standby position at which the sublimable substance-containing liquid nozzle  39  is located around the processing cup  21  in a plan view. 
     Similarly, the replacing liquid nozzle  43  is connected to a nozzle moving unit  46  that moves the replacing liquid nozzle  43  at least in one of the vertical and horizontal directions. The nozzle moving unit  46  horizontally moves the replacing liquid nozzle  43  between the processing position, at which the replacing liquid discharged from the replacing liquid nozzle  43  is supplied to the upper surface of the substrate W, and the standby position at which the replacing liquid nozzle  43  is located around the processing cup  21  in a plan view. 
     The processing unit  2  includes a shielding member  51  that is disposed above the spin chuck  10 .  FIG. 2  shows an example in which the shielding member  51  is a disc-shaped shielding plate. The shielding member  51  includes a disc portion  52  that is horizontally disposed above the spin chuck  10 . The shielding member  51  is horizontally supported by a tubular support shaft  53  that extends upwardly from the center portion of the disc portion  52 . The center line of the disc portion  52  is disposed on the rotation axis A 1  of the substrate W. The lower surface of the disc portion  52  corresponds to the lower surface  51 L of the shielding member  51 . The lower surface  51 L of the shielding member  51  is an opposing surface that faces the upper surface of the substrate W. The lower surface  51 L of shielding member  51  is parallel to the upper surface of the substrate W, and has an outer diameter that is greater than or equal to the diameter of the substrate W. 
     The shielding member  51  is connected to a shielding member elevating/lowering unit  54  that vertically elevates or lowers the shielding member  51 . The shielding member elevating/lowering unit  54  locates the shielding member  51  at an arbitrary position within a range from the upper position (the position shown in  FIG. 2 ) to the lower position. The lower position is the proximity position at which the shielding member  51  is located at a height in which the lower surface  51 L of the shielding member  51  comes into proximity to the upper surface of the substrate W and a scan nozzle such as the chemical liquid nozzle  31  cannot enter between the substrate W and the shielding member  51 . The upper position is the separate position at which the shielding member  51  retracts to a height in which the scan nozzle is able to enter between the shielding member  51  and the substrate W. 
     The plurality of nozzles include a central nozzle  55  that downwardly discharges a processing fluid such as a processing liquid or a processing gas through an upper central opening  61  that is opened at the center portion of the lower surface  51 L of the shielding member  51 . The central nozzle  55  extends vertically along the rotation axis A 1 . The central nozzle  55  is disposed inside a through-hole that vertically penetrates the center portion of the shielding member  51 . The inner circumferential surface of the shielding member  51  surrounds the outer circumferential surface of the central nozzle  55  across an interval in the radial direction (in the direction orthogonal to the rotation axis A 1 ). The central nozzle  55  is elevated or lowered together with the shielding member  51 . The discharge port of the central nozzle  55  to discharge the processing fluid is disposed above the upper central opening  61  of the shielding member  51 . 
     The central nozzle  55  is connected to an upper gas piping  56  that guides an inert gas to the central nozzle  55 . The substrate processing apparatus  1  may include an upper thermoregulator  59  that heats or cools the inert gas to be discharged from the central nozzle  55 . When an upper gas valve  57  interposed in the upper gas piping  56  is opened, the inert gas is continuously discharged downwardly from the discharge port of the central nozzle  55  at a flow rate corresponding to the opening degree of a flow rate adjusting valve  58  that changes the flow rate of the inert gas. The inert gas discharged from the central nozzle  55  is a nitrogen gas. The inert gas may be a gas other than the nitrogen gas such as a helium gas or an argon gas. 
     The inner circumferential surface of the shielding member  51  and the outer circumferential surface of the central nozzle  55  define a tubular upper gas flow passage  62  that extends vertically. The upper gas flow passage  62  is connected to an upper gas piping  63  that guides the inert gas to the upper central opening  61  of the shielding member  51 . The substrate processing apparatus  1  may include an upper thermoregulator  66  that heats or cools the inert gas to be discharged from the upper central opening  61  of the shielding member  51 . When an upper gas valve  64  interposed in the upper gas piping  63  is opened, the inert gas is continuously discharged downwardly from the upper central opening  61  of the shielding member  51  at a flow rate corresponding to the opening degree of a flow rate adjusting valve  65  that changes the flow rate of the inert gas. The inert gas discharged from the upper central opening  61  of the shielding member  51  is a nitrogen gas. The inert gas may be a gas other than the nitrogen gas such as a helium gas or an argon gas. 
     The plurality of nozzles include a lower-surface nozzle  71  that discharges the processing liquid to the center portion of the lower surface of the substrate W. The lower-surface nozzle  71  includes a nozzle disc portion that is disposed between the upper surface  12   u  of the spin base  12  and the lower surface of the substrate W, and a nozzle cylindrical portion that downwardly extends from the nozzle disc portion. The discharge port of the lower-surface nozzle  71  is opened at the center portion of the upper surface of the nozzle disc portion. When the substrate W is held on the spin chuck  10 , the discharge port of the lower-surface nozzle  71  vertically faces the center portion of the lower surface of the substrate W. 
     The lower-surface nozzle  71  is connected to a heating fluid piping  72  that guides hot water (pure water at a temperature higher than the room temperature) serving as an example of heating fluid to the lower-surface nozzle  71 . The pure water supplied to the lower-surface nozzle  71  is heated by a heater  75  that is interposed in the heating fluid piping  72 . When a heating fluid valve  73  interposed in the heating fluid piping  72  is opened, the hot water is discharged continuously upwardly from the discharge port of the lower-surface nozzle  71  at a flow rate corresponding to the opening degree of a flow rate adjusting valve  74  that changes the flow rate of the hot water. This allows the hot water to be supplied to the lower surface of the substrate W. 
     Furthermore, the lower-surface nozzle  71  is connected to a cooling fluid piping  76  that guides cold water (pure water at a temperature lower than the room temperature) serving as an example of cooling fluid to the lower-surface nozzle  71 . The pure water supplied to the lower-surface nozzle  71  is cooled by a cooler  79  interposed in the cooling fluid piping  76 . When a cooling fluid valve  77  interposed in the cooling fluid piping  76  is opened, the cold water is continuously discharged upwardly from the discharge port of the lower-surface nozzle  71  at a flow rate associated with the opening degree of a flow rate adjusting valve  78  that changes the flow rate of the cold water. This allows the cold water to be supplied to the lower surface of the substrate W. 
     The outer circumferential surface of the lower-surface nozzle  71  and the inner circumferential surface of the spin base  12  define a tubular lower gas flow passage  82  that extends vertically. The lower gas flow passage  82  includes a lower central opening  81  that is opened at the center portion of the upper surface  12   u  of the spin base  12 . The lower gas flow passage  82  is connected to a lower gas piping  83  that guides the inert gas to the lower central opening  81  of the spin base  12 . The substrate processing apparatus  1  may include a lower thermoregulator  86  that heats or cools the inert gas to be discharged from the lower central opening  81  of the spin base  12 . When a lower gas valve  84  interposed in the lower gas piping  83  is opened, the inert gas is continuously discharged upwardly from the lower central opening  81  of the spin base  12  at a flow rate corresponding to the opening degree of a flow rate adjusting valve  85  that changes the flow rate of the inert gas. 
     The inert gas discharged from the lower central opening  81  of the spin base  12  is a nitrogen gas. The inert gas may be a gas other than the nitrogen gas such as a helium gas or an argon gas. When the lower central opening  81  of the spin base  12  discharges the nitrogen gas with the substrate W held on the spin chuck  10 , the nitrogen gas radially flows in all directions between the lower surface of the substrate W and the upper surface  12   u  of the spin base  12 . This allows the space between the substrate W and the spin base  12  to be filled with the nitrogen gas. 
     Next, description will be made to a sublimable substance-containing liquid supplying unit  99 . 
       FIG. 3  is a schematic view showing a sublimable substance-containing liquid supplying unit  99  provided in the substrate processing apparatus  1 .  FIG. 4  is cross-sectional views showing examples of a cross-section of the substrate to be processed by the substrate W processing apparatus  1 . 
     As shown in  FIG. 3 , the substrate processing apparatus  1  includes the sublimable substance-containing liquid supplying unit  99  that supplies the sublimable substance-containing liquid to the substrate W held by the spin chuck  10 . The sublimable substance-containing liquid nozzle  39 , the sublimable substance-containing liquid piping  40 , and the sublimable substance-containing liquid valve  41  described above are contained in the sublimable substance-containing liquid supplying unit  99 . 
     The sublimable substance-containing liquid supplying unit  99  includes an undiluted liquid tank  87  that stores the sublimable substance-containing liquid corresponding to a undiluted liquid, a circulation piping  88  that circulates the sublimable substance-containing liquid in the undiluted liquid tank  87 , a pump  89  that sends the sublimable substance-containing liquid in the undiluted liquid tank  87  to the circulation piping  88 , and an individual piping  90  that guides the sublimable substance-containing liquid in the circulation piping  88  to the sublimable substance-containing liquid piping  40 . The sublimable substance-containing liquid supplying unit  99  further includes an opening and closing valve  91  that opens and closes the interior of the individual piping  90  and a flow rate adjusting valve  92  that changes the flow rate of the sublimable substance-containing liquid to be supplied to the sublimable substance-containing liquid piping  40  from the individual piping  90 . 
     The sublimable substance-containing liquid supplying unit  99  includes a diluting liquid tank  93  that stores a diluting liquid to dilute the sublimable substance-containing liquid. The diluting liquid is a solvent having the same name as that of the solvent contained in the sublimable substance-containing liquid in the undiluted liquid tank  87 , for example. a diluting liquid supplying unit includes a circulation piping  94  that circulates the diluting liquid in the diluting liquid tank  93 , a pump  95  that sends the diluting liquid in the diluting liquid tank  93  to the circulation piping  94 , and an individual piping  96  that guides the diluting liquid in the circulation piping  94  to the sublimable substance-containing liquid piping  40 . The diluting liquid supplying unit further includes an opening and closing valve  97  that opens and closes the interior of the individual piping  96  and a flow rate adjusting valve  98  that changes the flow rate of the diluting liquid to be supplied to the sublimable substance-containing liquid piping  40  from the individual piping  96 . 
     When the opening and closing valve  91  is opened, the sublimable substance-containing liquid is supplied to the sublimable substance-containing liquid piping  40  at a flow rate corresponding to the opening degree of the flow rate adjusting valve  92 . When the opening and closing valve 97  is opened, the diluting liquid is supplied to the sublimable substance-containing liquid piping  40  at a flow rate corresponding to the opening degree of the flow rate adjusting valve  98 . When both of the opening and closing valve  91  and the opening and closing valve  97  are opened, the sublimable substance-containing liquid supplied from the undiluted liquid tank  87  is mixed with the diluting liquid supplied from the diluting liquid tank  93  at the inside of the sublimable substance-containing liquid piping  40  and diluted. Thus, the diluted sublimable substance-containing liquid is discharged from the sublimable substance-containing liquid nozzle  39 . 
     The controller  3  sets the opening degrees of the opening and closing valve  91 , the flow rate adjusting valve  92 , the opening and closing valve  97 , and the flow rate adjusting valve  98  based on a concentration of the sublimable substance-containing liquid (a concentration of the sublimable substance) specified in a recipe described below. For example, in a case where the concentration of the sublimable substance-containing liquid specified in the recipe matches the concentration of the sublimable substance-containing liquid in the undiluted liquid tank  87 , the opening and closing valve  91  is opened and the opening and closing valve  97  is closed. In a case where the concentration of the sublimable substance-containing liquid specified in the recipe is lower than the concentration of the sublimable substance-containing liquid in the undiluted liquid tank  87 , both of the opening and closing valve  91  and the opening and closing valve  97  are opened and the opening degrees of the flow rate adjusting valve  92  and the flow rate adjusting valve  98  are adjusted. Thus, the concentration of the sublimable substance-containing liquid to be discharged from the sublimable substance-containing liquid nozzle  39  is approached to the concentration of the sublimable substance-containing liquid specified in the recipe. 
     The sublimable substance-containing liquid is selected according to the substrate W to be processed by the substrate processing apparatus  1  and stored in the undiluted liquid tank  87  before the processing of the substrate W at the substrate processing apparatus  1  is started. In a case where a surface of a pattern P 1  (refer to  FIG. 4 ) formed on a front surface of the substrate W is hydrophilic, a sublimable substance including a hydrophilic group and a solvent for hydrophilicity having less solubility in water than that of this sublimable substance are selected. In a case where the surface of a pattern P 1  formed on a front surface of the substrate W is hydrophobic, a sublimable substance including a hydrophobic group and a solvent for hydrophobicity having less solubility in water than that of this sublimable substance are selected. After that, the selected sublimable substance is dissolved in the selected solvent. Thus, the sublimable substance-containing liquid containing the selected sublimable substance and solvent is manufactured. The dissolution of the sublimable substance in the solvent may be conducted in the undiluted liquid tank  87 , or may be conducted in a tank different from the undiluted liquid tank  87 . 
     The sublimable substance-containing liquid in the undiluted liquid tank  87  may contain two or more kinds of the sublimable substances, or may contain two or more kinds of the solvents. The sublimable substance-containing liquid in the undiluted liquid tank  87  may further contain a substance other than the sublimable substance and the solvent. For example, an amphiphilic molecule including both of a hydrophilic group and a hydrophobic group may be contained in the sublimable substance-containing liquid. In this case, the solvent does not have to be a substance including a hydrophilic group and a hydrophobic group in the molecule such as alcohol. 
     In a case where the surface of the pattern P 1  is hydrophilic and two or more kinds of the sublimable substances are contained in the sublimable substance-containing liquid, at least one kind of the sublimable substance may contain a hydrophilic group. In this case, the solubility of the solvent in water may be smaller than the solubility of the sublimable substance including a hydrophilic group in water. In a case where the surface of the pattern P 1  is hydrophilic and two or more kinds of the solvents are contained in the sublimable substance-containing liquid, the solubilities of all kinds of the solvents in water are preferably smaller than the solubility of the sublimable substance including a hydrophilic group in water. 
     In a case where the surface of the pattern P 1  is hydrophobic and two or more kinds of the sublimable substances are contained in the sublimable substance-containing liquid, at least one kind of the sublimable substance may contain a hydrophobic group. In this case, the solubility of the solvent in oil may be smaller than the solubility of the sublimable substance including a hydrophobic group in oil. In a case where the surface of the pattern P 1  is hydrophobic and two or more kinds of the solvents are contained in the sublimable substance-containing liquid, the solubilities of all kinds of the solvents in oil are preferably smaller than the solubility of the sublimable substance including a hydrophobic group in water. 
     In a case where the surface of the pattern P 1  is hydrophilic, the sublimable substance-containing liquid may be a solution consisting of camphor , tertiary butyl alcohol, and IPA or a solution consisting of camphor, IPA, the first solute, the second solute, and the first solvent, or may be a solution other than these. The followings are specific examples of the first solute, the second solute, and the first solvent. In a case where the surface of the pattern P 1  is hydrophobic, the sublimable substance-containing liquid may be a solution consisting of camphor and IPA or a solution consisting of camphor and methanol, or may be a solution other than these. Camphor is the sublimable substance including a methyl group, which is an example of the hydrophobic group, in its molecule. Tertiary butyl alcohol is the sublimable substance including a methyl group, which is an example of the hydrophobic group, and a hydroxy group, which is an example of the hydrophilic group, in its molecule. 
     Each of the first solute and the second solute is a single substance. The first solute and the second solute are substances different from each other. Each of the first solute and the second solute has at least one of an amino group, a hydroxy group and a carbonyl group. 
     Each of the first solute and the second solute is any of phthalic anhydride, caffeine, melamine, 1,4-benzoquinone, camphor, hexamethylenetetramine,1,3,5-trimethylhexahydro-1,3,5-triazine, 1-adamantanol, 1,4-diazabicyclo[2.2.2]octane, borneol, (×)-borneol, (±)-isoborneol, 1,2-cyclohexanedione, 1,3-cyclohexanedione, 1, 4-cyclohexanedione, 3-methyl-1,2-cyclopentanedione, (±)-camphorquinone, (−)-camphorquinone, (+)-camphorquinone, and 1-adamantanamine. 
     The first solvent does not have to include pure water, or may include pure water and one or more kinds of substances other than pure water. The first solvent may include organic solvent. The organic solvent may be a single substance, or may be two or more kinds of substances mixed with each other. 
     Examples of the organic solvent include alcohol such as methanol (MeOH), ethanol (Et 0 H), or isopropanol (IPA), alkane such as hexane, heptane, or octane, ether such as butyl ethyl ether, dibutyl ether, or tetrahydrofuran (THF), lactic acid ester such as methyl lactate, or ethyl lactate (EL), aromatic hydrocarbon such as benzene, toluene, or xylene, ketone such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, cyclopentanone, or cyclohexanone, amide such as N,N-dimethylacetamide, or N-methylpyrrolidone, lactone such as gamma-butyrolactone. 
     Other examples of the ether include ethylene glycol monoalkylether such as ethylene glycol monomethyl ether, or ethylene glycol monohexyl ether, ethylene glycol monoalkyl ether acetate such as ethylene glycol monomethyl ether acetate, or ethylene glycol monoethyl ether acetate, propylene glycol monoalkyl ether such as propylene glycol monomethyl ether (PGME), or propylene glycol monoethyl Ether (PGEE), propylene glycol monoalkyl ether acetate such as propylene glycol monomethyl ether acetate (PGMEA), or propylene glycol monoethyl ether acetate. 
     As shown in  FIG. 4( a ) , in a case where an entire surface of the pattern P 1 , that is, an entire upper surface Pu of the pattern P 1  and an entire side surface Ps of the pattern P 1  have the same properties, if any portion of the surface of the pattern P 1  is hydrophilic, the surface of the pattern P 1  is determined to be hydrophilic. In a case where the entire surface of the pattern P 1  has the same properties, if any portion of the surface of the pattern P 1  is hydrophobic, the surface of the pattern P 1  is determined to be hydrophobic. In this case, if the contact angle of water with respect to the surface of the pattern P 1  is, for example, 60 degrees or less, the surface of the pattern P 1  is determined to be hydrophilic. In a case where the entire surface of the pattern P 1  has the same properties, the pattern P 1  may be either a monolayer film or a laminated film. 
     On the other side, as shown in  FIG. 4  (b), when a hydrophilic portion and a hydrophobic portion are included in the surface of the pattern P 1 , and an upper end portion Px of the side surface Ps of the pattern P 1  is hydrophilic, the surface of the pattern P 1  is regarded as hydrophilic. When the hydrophilic portion and the hydrophobic portion are included in the surface of the pattern P 1 , and an upper end portion Px of the side surface Ps of the pattern P 1  is hydrophobic, the surface of the pattern P 1  is regarded as hydrophobic. That is, in a case where the hydrophilic portion and the hydrophobic portion are included in the surface of the pattern P 1 , it is determined whether the surface of the pattern P 1  is hydrophilic or hydrophobic based on the property of the upper end portion Px of the side surface Ps of the pattern P 1 . 
       FIG. 5  is a block diagram showing the hardware of the controller  3 . 
     The controller  3  is a computer which includes a computer main body  3   a  and a peripheral device  3   d  which is connected to the computer main body  3   a . The computer main body  3   a  includes a CPU  3   b  (central processing unit) which executes various types of commands and a main storage device  3   c  which stores information. The peripheral device  3   d  includes an auxiliary storage device  3   e which stores information such as a program P, a reading device  3   f  which reads information from a removable medium RM and a communication device  3   g  which communicates with other devices such as a host computer. 
     The controller  3  is connected to an input device and a display. The input device is operated when an operator such as a user or a maintenance operator inputs information to the substrate processing apparatus  1 . The information is displayed on the screen of the display. The input device may be any one of a keyboard, a pointing device and a touch panel or may be a device other than those. A touch panel display which serves both as the input device and the display may be provided in the substrate processing apparatus  1 . 
     The CPU  3   b  executes the program P stored in the auxiliary storage device  3   e . The program P within the auxiliary storage device  3   e  may be previously installed in the controller  3 , may be fed through the reading device  3   f  from the removable medium RM to the auxiliary storage device  3   e  or may be fed from an external device such as the host computer to the auxiliary storage device  3   e  through the communication device  3   g.    
     The auxiliary storage device  3   e  and the removable medium RM are nonvolatile memories which retain memory even without power being supplied. The auxiliary storage device  3   e  is, for example, a magnetic storage device such as a hard disk drive. The removable medium RM is, for example, an optical disc such as a compact disc or a semiconductor memory such as a memory card. The removable medium RM is an example of a computer readable recording medium in which the program P is recorded. The removable medium RM is a non-transitory tangible recording medium. 
     The auxiliary storage device  3   e  stores a plurality of recipes. The recipe is information which specifies the details of processing, processing conditions and processing procedures of the substrate W. A plurality of recipes differ from each other in at least one of the details of processing, the processing conditions, and the processing procedures of the substrate W. The controller  3  controls the substrate processing apparatus  1  such that the substrate W is processed according to the recipe designated by the host computer. The controller  3  is programmed to execute the individual steps described below. 
       FIG. 6  is a process chart for describing an example of the processing of the substrate W which is executed by the substrate processing apparatus  1 .  FIG. 2  and  FIG. 6  shall be referenced in the following. 
     For example, the substrate W to be processed is a semiconductor wafer such as a silicon wafer. The front surface of the substrate W corresponds to the device formation surface on which devices such as transistors or capacitors are formed. The substrate W may be a substrate W having patterns P 1  (see  FIG. 7A ) formed on the front surface of the substrate W corresponding to a pattern formation surface, or alternatively, may be a substrate W having no patterns P 1  formed on the front surface of the substrate W. In the latter case, the patterns P 1  may be formed in a chemical liquid supplying step described below. 
     When the substrate W is processed by the substrate processing apparatus  1 , a carry-in step (step S 1  in  FIG. 6 ) is performed to carry the substrate W into the chamber  4 . 
     Specifically, while the shielding member  51  is located at the upper position, all the guards  24  are located at the lower position, and all scan nozzles are located at the standby position, the center robot CR (see  FIG. 1A ) causes a hand H 1  to enter the chamber  4  while supporting the substrate W with the hand H 1 . Then, the center robot CR places the substrate W in the hand H 1  on the plurality of chuck pins  11  while the front surface of the substrate W is directed upwardly. Thereafter, the plurality of chuck pins  11  are pushed against the outer circumferential surface of the substrate W to thereby grip the substrate W. The center robot CR retracts the hand H 1  out of the chamber  4  after having placed the substrate W on the spin chuck  10 . 
     Next, the upper gas valve  64  and the lower gas valve  84  are opened, and the upper central opening  61  of the shielding member  51  and the lower central opening  81  of the spin base  12  start to discharge the nitrogen gas. This allows the space between the substrate W and the shielding member  51  to be filled with the nitrogen gas. Similarly, the space between the substrate W and the spin base  12  is filled with the nitrogen gas. Meanwhile, the guard elevating/lowering unit  27  elevates at least one guard  24  from the lower position to the upper position. Thereafter, the spin motor  14  is driven, and the rotation of the substrate W is started (step S 2  in  FIG. 6 ). This allows the substrate W to be rotated at a liquid supplying speed. 
     Next, the chemical liquid supplying step (step S 3  in  FIG. 6 ) is performed to supply a chemical liquid onto the upper surface of the substrate W and thereby form a liquid film of the chemical liquid that covers the entire upper surface of the substrate W. 
     Specifically, with the shielding member  51  located at the upper position and at least one guard  24  located at the upper position, the nozzle moving unit  34  moves the chemical liquid nozzle  31  from the standby position to the processing position. Thereafter, the chemical liquid valve  33  is opened, and the chemical liquid nozzle  31  starts to discharge the chemical liquid. When a predetermined time has elapsed after the chemical liquid valve  33  is opened, the chemical liquid valve  33  is closed, so that the discharge of the chemical liquid is stopped. Thereafter, the nozzle moving unit  34  moves the chemical liquid nozzle  31  to the standby position. 
     The chemical liquid discharged from the chemical liquid nozzle  31  collides with the upper surface of the substrate W that is rotating at the liquid supplying speed, and then, flows outwardly along the upper surface of the substrate W due to centrifugal force. Thus, the chemical liquid is supplied to the entire upper surface of the substrate W to thereby form the liquid film of the chemical liquid that covers the entire upper surface of the substrate W. While the chemical liquid nozzle  31  is discharging the chemical liquid, the nozzle moving unit  34  may move a liquid landing position so that the liquid landing position of the chemical liquid passes the center portion and the outer circumference portion of the upper surface of the substrate W, or alternatively, may bring the liquid landing position to a standstill at the center portion. 
     Next, a rinse liquid supplying step (step S 4  in  FIG. 6 ) is performed to supply pure water serving as an example of rinse liquid to the upper surface of the substrate W and thereby wash away the chemical liquid on the substrate W. 
     Specifically, with the shielding member  51  located at the upper position and at least one guard  24  located at the upper position, the nozzle moving unit  38  moves the rinse liquid nozzle  35  from the standby position to the processing position. Thereafter, the rinse liquid valve  37  is opened, and the rinse liquid nozzle  35  starts to discharge the rinse liquid. Before the pure water starts to be discharged, the guard elevating/lowering unit  27  may vertically move at least one guard  24  in order to switch the guard  24  that receives the liquid discharged from the substrate W. When a predetermined time has elapsed after the rinse liquid valve  37  is opened, the rinse liquid valve  37  is closed, so that the discharge of the rinse liquid is stopped. Thereafter, the nozzle moving unit  38  moves the rinse liquid nozzle  35  to the standby position. 
     The pure water discharged from the rinse liquid nozzle  35  collides with the upper surface of the substrate W that is rotating at the liquid supplying speed, and then, flows outwardly along the upper surface of the substrate W due to centrifugal force. The chemical liquid on the substrate W is replaced with the pure water discharged from the rinse liquid nozzle  35 . This allows a liquid film of the pure water covering the entire upper surface of the substrate W to be formed. While the rinse liquid nozzle  35  is discharging the pure water, the nozzle moving unit  38  may move a liquid landing position so that the liquid landing position of the pure water passes the center portion and the outer circumference portion of the upper surface of the substrate W, or alternatively, may bring the liquid landing position to a standstill at the center portion. 
     Next, a replacing liquid supplying step (step S 5  in  FIG. 6 ) is performed to supply a replacing liquid that dissolves with both the rinse liquid and the sublimable substance-containing liquid to the upper surface of the substrate W and then replace the pure water on the substrate W with the replacing liquid. 
     Specifically, with the shielding member  51  located at the upper position and at least one guard  24  located at the upper position, the nozzle moving unit  46  moves the replacing liquid nozzle  43  from the standby position to the processing position. Thereafter, the replacing liquid valve  45  is opened, and the replacing liquid nozzle  43  starts to discharge the replacing liquid. Before the replacing liquid starts to be discharged, the guard elevating/lowering unit  27  may vertically move at least one guard  24  in order to switch the guard  24  that receives the liquid discharged from the substrate W. When a predetermined time has elapsed after the replacing liquid valve  45  is opened, the replacing liquid valve  45  is closed, so that the discharge of the replacing liquid is stopped. Thereafter, the nozzle moving unit  46  moves the replacing liquid nozzle  43  to the standby position. 
     The replacing liquid discharged from the replacing liquid nozzle  43  collides with the upper surface of the substrate W that is rotating at the liquid supplying speed, and then, flows outwardly along the upper surface of the substrate W due to centrifugal force. The pure water on the substrate W is replaced with the replacing liquid discharged from the replacing liquid nozzle  43 . This allows a liquid film of the replacing liquid covering the entire upper surface of the substrate W to be formed. While the replacing liquid nozzle  43  is discharging the replacing liquid, the nozzle moving unit  46  may move a liquid landing position so that the liquid landing position of the replacing liquid passes the center portion and the outer circumference portion of the upper surface of the substrate W, or alternatively, may bring the liquid landing position to a standstill at the center portion. After the liquid film of the replacing liquid covering the entire upper surface of the substrate W is formed, the substrate W may be rotated at a paddle speed (e.g., at a speed greater than zero and  20 rpm or less) while the discharge of the replacing liquid from the replacing liquid nozzle  43  is stopped. 
     Next, a sublimable substance-containing liquid supplying step (step S 6  in  FIG. 6 ) is performed to supply the sublimable substance-containing liquid to the upper surface of the substrate W and thereby form a liquid film of the sublimable substance-containing liquid on the substrate W. 
     Specifically, with the shielding member  51  located at the upper position and at least one guard  24  located at the upper position, the nozzle moving unit  42  moves the sublimable substance-containing liquid nozzle  39  from the standby position to the processing position. Thereafter, the sublimable substance-containing liquid valve  41  is opened, and the sublimable substance-containing liquid nozzle  39  starts to discharge the sublimable substance-containing liquid. Before the sublimable substance-containing liquid starts to be discharged, the guard elevating/lowering unit  27  may vertically move at least one guard  24  in order to switch the guard  24  that receives the liquid discharged from the substrate W. When a predetermined time has elapsed after the sublimable substance-containing liquid valve  41  is opened, the sublimable substance-containing liquid valve  41  is closed, so that the discharge of the sublimable substance-containing liquid is stopped. Thereafter, the nozzle moving unit  42  moves the sublimable substance-containing liquid nozzle  39  to the standby position. 
     The sublimable substance-containing liquid discharged from the sublimable substance-containing liquid nozzle  39  collides with the upper surface of the substrate W that is rotating at the liquid supplying speed, and then, flows outwardly along the upper surface of the substrate W due to centrifugal force. The replacing liquid on the substrate W is replaced with the sublimable substance-containing liquid discharged from the sublimable substance-containing liquid nozzle  39 . This allows a liquid film of the sublimable substance-containing liquid covering the entire upper surface of the substrate W to be formed. While the sublimable substance-containing liquid nozzle  39  is discharging the sublimable substance-containing liquid, the nozzle moving unit  42  may move a liquid landing position so that the liquid landing position of the sublimable substance-containing liquid passes the center portion and the outer circumference portion of the upper surface of the substrate W, or alternatively, may bring the liquid landing position to a standstill at the center portion. 
     Next, a film thickness decreasing step (step S 7  in  FIG. 6 ) is performed to remove some of the sublimable substance-containing liquid on the substrate W and decrease the film thickness (the thickness of the liquid film) of the sublimable substance-containing liquid on the substrate W while maintaining the state that the entire upper surface of the substrate W is covered with the liquid film of the sublimable substance-containing liquid. 
     Specifically, with the shielding member  51  located at the lower position, the spin motor  14  maintains the rotational speed of the substrate W at a film thickness decreasing speed. The film thickness decreasing speed may be equal to or different from the liquid supplying speed. The sublimable substance-containing liquid on the substrate W is discharged outwardly from the substrate W due to centrifugal force even after the discharge of the sublimable substance-containing liquid is stopped. Thus, the thickness of the liquid film of the sublimable substance-containing liquid on the substrate W is decreased. When the sublimable substance-containing liquid on the substrate W is discharged to a certain extent, the amount of the sublimable substance-containing liquid discharged from the substrate W per unit time is reduced to zero or generally zero. Thereby, the thickness of the liquid film of the sublimable substance-containing liquid on the substrate W is stabilized at a value corresponding to the rotational speed of the substrate W. 
     Next, a solidified film forming step (step S 8  in  FIG. 6 ) is performed to evaporate the solvent from the sublimable substance-containing liquid on the substrate W and to form a solidified film SF (refer to  FIG. 76 ), which includes the sublimable substance, on the substrate W. 
     Specifically, with the shielding member  51  located at the lower position, the spin motor  14  maintains the rotational speed of the substrate W at a solidified film forming speed. The solidified film forming speed may be equal to or different from the liquid supplying speed. Furthermore, the upper gas valve  57  is opened and the central nozzle  55  starts to discharge the nitrogen gas. The flow rate of the nitrogen gas to be discharged from the upper central opening  61  of the shielding member  51  may be increased by changing the opening degree of the flow rate adjusting valve  65 , in addition to or instead of opening the upper gas valve  57 . 
     When the rotation of the substrate W at the solidified film forming speed and so on are started, the evaporation of the sublimable substance-containing liquid is facilitated and some of the sublimable substance-containing liquid on the substrate W evaporates. Since the vapor pressure of the solvent is higher than the vapor pressure of the sublimable substance corresponding to the solute, the solvent evaporates at an evaporation speed higher than an evaporation speed of the sublimable substance. Thus, the film thickness of the sublimable substance-containing liquid gradually decreases while the concentration of the sublimable substance gradually increases. The freezing point of the sublimable substance-containing liquid rises as the concentration of sublimable material rises. When the freezing point of the sublimable substance-containing liquid matches the temperature of the sublimable substance-containing liquid, the sublimable substance-containing liquid starts to solidify and the solidified film SF corresponding to a solidified body covering the entire upper surface of the substrate W is formed. 
     Next, a sublimating step (step S 9  in  FIG. 6 ) is performed to sublimate the solidified film SF on the substrate W and remove it from the upper surface of the substrate W. 
     Specifically, with the shielding member  51  located at the lower position, the spin motor  14  maintains the rotational speed of the substrate W at a sublimating speed. The sublimating speed may be equal to or different from the liquid supplying speed. Furthermore, in a case where the upper gas valve  57  is closed, the upper gas valve  57  is opened and the central nozzle  55  starts to discharge the nitrogen gas. In addition to or in place of opening the upper gas valve  57 , the opening degree of the flow rate adjusting valve  65  may be changed to increase the flow rate of the nitrogen gas discharged from the upper central opening  61  of the shielding member  51 . When a predetermined time has elapsed after the rotation of the substrate W at the sublimating speed is started, the spin motor  14  stops and the rotation of the substrate W is stopped (step S 10  in  FIG. 6 ). 
     When the rotation of the substrate W at the sublimating speed and so on are started, the solidified film SF on the substrate W starts to sublimate, so that a gas containing a sublimable substance is generated from the solidified film SF on the substrate W. The gas generated from the solidified film SF (a gas containing the sublimable substance) radially flows through the space between the substrate W and the shielding member  51  and is removed from the space over the substrate W. When a certain time has elapsed after the sublimating started, all of the solidified film SF is removed from the substrate W. 
     Next, a carry-out step (step S 11  in  FIG. 6 ) is performed to carry the substrate W out of the chamber  4 . 
     Specifically, the shielding member elevating/lowering unit  54  elevates the shielding member  51  to the upper position, and the guard elevating/lowering unit  27  lowers all the guards  24  to the lower position. Furthermore, the upper gas valve  64  and the lower gas valve  84  are closed, so that the upper central opening  61  of the shielding member  51  and the lower central opening  81  of the spin base  12  stop discharging the nitrogen gas. Thereafter, the center robot CR causes the hand H 1  to enter the chamber  4 . After the plurality of chuck pins  11  release the gripping of the substrate W, the center robot CR supports the substrate W on the spin chuck  10  with the hand H 1 . Thereafter, while supporting the substrate W with the hand H 1 , the center robot CR retracts the hand H 1  out of the chamber  4 . This allows the processed substrate W to be carried out of the chamber  4 . 
       FIG. 7A  to  FIG. 7F  are schematic views for describing phenomena that are expected to occur in the processing of the substrate W shown in  FIG. 6  during the period of time from supplying the upper surface of the substrate W with the sublimable substance-containing liquid to removing the solidified film SF from the upper surface of the substrate W. 
     In the following, a case where the entire surface of the pattern P 1  is hydrophilic and the sublimable substance, which includes the hydrophilic group, and IPA serving as the solvent are contained in the sublimable substance-containing liquid will be described. In the description below, it is to be understood that the solubility of the sublimable substance having the hydrophilic group in water is larger than the solubility of IPA in water. 
     As shown in  FIG. 7A , the sublimable substance-containing liquid is supplied to the upper surface of the substrate W with the substrate W rotating and the upper surface of the substrate W covered with a liquid film of the replacing liquid. Thus, as shown in  FIG. 76 , the replacing liquid is discharged from areas between the patterns P 1  and the areas between the patterns P 1  are filled with the sublimable substance-containing liquid.  FIG. 7C  shows the distribution of the sublimable substances in the sublimable substance-containing liquid supplied to the upper surface of the substrate W. In  FIG. 7C , the sublimable substances are represented by circles. 
     A single molecule of IPA includes a hydroxy group, which is an example of the hydrophilic group, and two methyl groups which are an example of the hydrophobic group. Thus, while an attractive force is applied to IPA to attract it to the surface of the pattern P 1 , a repulsive force is also applied to IPA to keep it away from the surface of the pattern P 1 . Furthermore, the sublimable substance having the hydrophilic group has a higher affinity for the surface of the pattern P 1  than IPA. Thus, it is considered that IPA is less likely to be retained on the surface of the pattern P 1 , compared to the sublimable substance. 
     As shown in  FIG. 7D , after the upper surface of the substrate W is covered with the liquid film of the sublimable substance-containing liquid, the solvent is evaporated from the sublimable substance-containing liquid on the substrate W. When the solvent evaporates, the concentration of the sublimable substance increases. The freezing point of the sublimable substance-containing liquid rises as the concentration of the sublimable substance rises. When the freezing point of the sublimable substance-containing liquid matches the temperature of the sublimable substance-containing liquid, as shown in  FIG. 7E , the solidification of the sublimable substance-containing liquid starts and the solidified film SF corresponding to the solidified body covering the entire upper surface of the substrate W is formed. After that, as shown in  FIG. 7F , the solidified film SF is sublimated and removed from the upper surface of the substrate W. 
     When the solidified film SF is being formed, the solvent is evaporated from a bulk portion (refer to  FIG. 7C ) of the liquid film of the sublimable substance-containing liquid, that is, a liquid layer located in a range from the upper surface (liquid surface) of the liquid film of the sublimable substance-containing liquid to the upper surface Pu of the pattern P 1 , and the concentration of the sublimable substance in the bulk portion of the liquid film rises. IPA contained in the sublimable substance-containing liquid existing between the patterns P 1  moves to the bulk portion of the liquid film and is released into the air from the upper surface of the sublimable substance-containing liquid. Thus, the concentration of the sublimable substance increases not only above the patterns P 1  but also between the patterns P 1 . Accordingly, as shown in  FIG. 7E , it is considered that after the solidified film SF is formed, the liquid IPA is discharged from between the patterns P 1  and an area between two adjacent projecting patterns P 1  is filled with the solidified film SF. 
       FIG. 8A  to  FIG. 8D  are cross-sectional views of the substrate W for describing phenomena that are expected to occur in the processing of the substrate W shown in  FIG. 6  during the period of time from supplying the upper surface of the substrate W with the sublimable substance-containing liquid to removing the solidified film SF from the upper surface of the substrate W. 
     In the following, a case where the entire surface of the pattern P 1  is hydrophilic and the sublimable substance, which includes the hydrophilic group, and methanol serving as the solvent are contained in the sublimable substance-containing liquid will be described. The processing conditions for the substrate W are the same as those for the substrate W described with reference to  FIG. 7A  to  FIG. 7F , except that the solvent is methanol instead of IPA. In the description below, it is to be understood that the solubility of the sublimable substance having the hydrophilic group in water is smaller than the solubility of methanol in water. 
     As with the processing of the substrate W described with reference to  FIG. 7A  to  FIG. 7F , the sublimable substance-containing liquid containing methanol serving as the solvent is supplied to the upper surface of the substrate W with the substrate W rotating and the upper surface of the substrate W covered with the liquid film of the replacing liquid. Thus, the replacing liquid is discharged from areas between the patterns P 1  and the areas between the patterns P 1  are filled with the sublimable substance-containing liquid.  FIG. 8A  shows a state where the areas between the patterns P 1  are filled the sublimable substance-containing liquid containing the sublimable substance and the solvent (methanol). 
     A single molecule of methanol includes a hydroxy group, which is an example of the hydrophilic group, and a methyl group which is an example of the hydrophobic group. Thus, while an attractive force is applied to methanol to attract it to the surface of the pattern P 1 , a repulsive force is also applied to methanol to keep it away from the surface of the pattern P 1 . However, compared to IPA, the number of the methyl groups contained in one molecule is small. Thus, it is considered that methanol is likely to be held by the surface of the pattern P 1  compared to IPA. Furthermore, the sublimable substance having the hydrophilic group has less affinity with respect to the surface of the pattern P 1  than methanol. Thus, it is considered that methanol is likely to be held by the surface of the pattern P 1  compared to the sublimable substance. 
     When the solidified film SF is being formed, methanol contained in the sublimable substance-containing liquid existing between the patterns P 1  moves to a bulk portion (refer to  FIG. 8A ) of the liquid film of the sublimable substance-containing liquid, and is released into the air from the upper surface of the sublimable substance-containing liquid. However, since the force to hold methanol on the surface of the pattern P 1  is relatively strong, it is difficult for methanol to be discharged from between the patterns P 1 . Thus, the concentration of the sublimable substance in the sublimable substance-containing liquid existing between the patterns P 1  does not rise easily. It is considered that ,due to this, methanol may remain between the patterns P 1  after the bulk portion of the liquid film changes to the solidified film SF.  FIG. 8B  shows an example where after the solidified film SF is formed above the patterns P 1 , the areas between the patterns P 1  are filled with methanol. 
     In the case of the example shown in  FIG. 8B , as shown in  FIG. 8C , methanol remains between the patterns P 1  even after the solidified film SF is sublimated. Methanol remaining between the patterns P 1  is removed from the substrate W by evaporation. However, until methanol is removed from the substrate W, a liquid surface (interface between gas and liquid) of methanol is formed between two adjacent projecting patterns P 1 , and the collapsing force to collapse the patterns P 1  is applied to the patterns P 1  from methanol. When the strength of the pattern P 1  is low, as shown in  FIG. 8D , the pattern P 1  collapses even with such a collapsing force. 
     In this way, if the surface of the pattern P 1  is hydrophilic and the solvent has strong hydrophilicity, when the solidified film SF is being formed, the solvent is not discharged from between the patterns P 1  and remains between the patterns P 1 , and the collapsing force to collapse the patterns P 1  is applied to the patterns P 1  from the solvent. Similarly, if the surface of the pattern P 1  is hydrophobic and the solvent has strong hydrophobicity, when the solidified film SF is being formed, the solvent is not discharged from between the patterns P 1  and remains between the patterns P 1 , and the collapsing force to collapse the patterns P 1  is applied to the patterns P 1  from the solvent. Thus, if the solvent is not selected in consideration of the affinity between the solvent and the pattern P 1 , the collapse of the pattern P 1  occurs depending on the strength of the pattern P 1 . 
     As described above, in the preferred embodiment, the sublimable substance-containing liquid containing the sublimable substance, which corresponds to the solute, and the solvent is supplied to the front surface of the substrate W on which the pattern P 1  is formed. After that, the solvent is evaporated from the sublimable substance-containing liquid. Thus, the solidified film SF including the sublimable substance is formed on the front surface of the substrate W. After that, the solidified film SF on the substrate W is changed to gas without passing through to a liquid. Thus, the solidified film SF is removed from the front surface of the substrate W. Accordingly, it is possible to lower the collapse rate of the patterns P 1  as compared to the conventional drying method such as spin drying. 
     In a case where the surface of the pattern P 1  is hydrophilic, the solvent having less solubility in water than that of the sublimable substance is contained in the sublimable substance-containing liquid. When the surface of the pattern P 1  is hydrophilic and the hydrophilicity of the solvent is high, the solvent is likely to be held on the surface of the pattern, so that a lot of the solvent remains between the patterns P 1  even after forming the solidified film SF. In this case, the collapsing force to collapse the pattern P 1  is applied to the pattern P 1  from the solvent. It is possible to reduce the solvent remaining between the patterns P 1  after forming the solidified film SF to zero or a value close to it by using the solvent having low hydrophilicity. 
     In a case where the surface of the pattern P 1  is hydrophobic, the solvent having less solubility in oil than that of the sublimable substance is contained in the sublimable substance-containing liquid. When the surface of the pattern P 1  is hydrophobic and the hydrophobicity of the solvent is high, the solvent is likely to be held on the surface of the pattern, so that a lot of the solvent remains between the patterns P 1  even after forming the solidified film SF. In this case, the collapsing force to collapse the pattern P 1  is applied to the pattern P 1  from the solvent. It is possible to reduce the solvent remaining between the patterns P 1  after forming the solidified film SF to zero or a value close to it by using the solvent having low hydrophobicity. 
     In this way, the solvent contained in the sublimable substance-containing liquid has less affinity with respect to the surface of the pattern P 1  than the sublimable substance contained in the sublimable substance-containing liquid regardless of whether the surface of the pattern P 1  is hydrophilic or hydrophobic. Thus, it is possible to reduce the solvent remaining between the patterns P 1  after forming the solidified film SF and to weaken the collapsing force applied to the pattern P 1  during and after the solidified film SF is formed. Accordingly, it is possible to dry the substrate W with the low collapse rate of the pattern P 1  regardless of whether the surface of the pattern P 1  is hydrophilic or hydrophobic. 
     In the preferred embodiment, in a case where the hydrophilic portion and the hydrophobic portion are included in the surface of the pattern, if the upper end portion Px of the side surface Ps of the pattern P 1  is hydrophilic, the surface of the pattern P 1  is regarded as hydrophilic. In a case where the hydrophilic portion and the hydrophobic portion are included in the surface of the pattern, if the upper end portion Px of the side surface Ps of the pattern P 1  is hydrophobic, the surface of the pattern P 1  is regarded as hydrophobic. That is, it is determined whether the surface of the pattern P 1  is hydrophilic or hydrophobic based on the property of the upper end portion Px of the side surface Ps of the pattern P 1 . 
     When a liquid surface (interface between gas and liquid) is formed between two adjacent projecting patterns P 1  , the collapsing force due to the surface tension is applied to the patterns P 1 . This collapsing force increases as a distance from the root of the pattern P 1  to the liquid surface increases. Thus, even when the liquid surface is formed between the two adjacent projecting patterns P 1  , if the distance from the root (lower end) of the pattern P 1  to the liquid surface is short, the collapsing force applied to the pattern P 1  is weak. 
     If the surface of the pattern P 1  is regarded as hydrophobic when the hydrophilic portion and the hydrophobic portion are included in the surface of the pattern P 1  and the upper end portion Px of the side surface Ps of the pattern P 1  is hydrophilic, it is likely that the liquid surface of the solvent is formed at the upper end portion Px of the side surface Ps of the pattern P 1  after forming the solidified film SF and the large collapsing force is applied to the pattern P 1 . If the surface of the pattern P 1  is regarded as hydrophilic, even when the liquid surface of the solvent is formed between the patterns P 1  , the liquid surface of the solvent is disposed on the root side of the pattern P 1 . Thus, it is possible to shorten the distance from the root of the pattern P 1  to the liquid surface. 
     For the same reason, if the surface of the pattern P 1  is regarded as hydrophobic when the hydrophilic portion and the hydrophobic portion are included in the surface of the pattern P 1  and the upper end portion Px of the side surface Ps of the pattern P 1  is hydrophobic, even when the liquid surface of the solvent is formed between the patterns P 1  , it is possible to shorten the distance from the root of the pattern P 1  to the liquid surface. Thus, it is possible to weaken the collapsing force applied to the pattern P 1  and to lower the collapse rate of the pattern P 1 . 
     Next, description will be made to a second preferred embodiment. 
     The second preferred embodiment is different from the first preferred embodiment mainly in that the sublimable substance-containing liquid is manufactured just before the sublimable substance-containing liquid is supplied to the substrate W. 
     In  FIG. 9  to  FIG. 10  below, the same components as those shown in  FIG. 1  to  FIG. 8D  will be given the same reference symbols as those of  FIG. 1  and so on, and the description thereof will be omitted. 
       FIG. 9  is a schematic view showing the sublimable substance-containing liquid supplying unit  99  provided in the substrate processing apparatus  1  according to the second preferred embodiment of the present invention. 
     The sublimable substance-containing liquid supplying unit  99  includes a first undiluted liquid tank  87 A that stores a liquid containing the sublimable substance and a second undiluted liquid tank  876  that stores a liquid containing the sublimable substance. The liquid in the first undiluted liquid tank  87 A contains the sublimable substance having the hydrophilic group. The liquid in the second undiluted liquid tank  876  contains the sublimable substance having the hydrophobic group. The liquid in the first undiluted liquid tank  87 A and the liquid in the second undiluted liquid tank  876  are different from each other in at least one component. The liquid in the first undiluted liquid tank  87 A may be a melt of the sublimable substance. If the concentration of the sublimable substance is high, the liquid in the first undiluted liquid tank  87 A may be a solution containing the sublimable substance and the solvent, or may contain the sublimable substance and a substance other than the solvent. The same applies to the liquid in the second undiluted liquid tank  876 . 
     The sublimable substance-containing liquid supplying unit  99  includes a first diluting liquid tank  93 A that stores the solvent and a second diluting liquid tank  93 B that stores the solvent. The solvent in the first diluting liquid tank  93 A and the solvent in the second diluting liquid tank  93 B are different from each other in at least one component. The solvent in the first diluting liquid tank  93 A may be a melt of the solvent, may be an aqueous solution of the solvent, or may contain the solvent and a substance other than the solvent. The same applies to the solvent in the second diluting liquid tank  93 B. The solvent in the first diluting liquid tank  93 A and the solvent in the second diluting liquid tank  93 B may be alcohol. 
     The liquid in the first undiluted liquid tank  87 A is sent to a circulation piping  88 A by a pump  89 A and returns to the first undiluted liquid tank  87 A from the circulation piping  88 A. The liquid in the second undiluted liquid tank  876  is sent to a circulation piping  88 B by a pump  89 B and returns to the second undiluted liquid tank  876  from the circulation piping  88 B. The circulation piping  88 A is connected to an individual piping  90 A in which an opening and closing valve  91 A and a flow rate adjusting valve  92 A are interposed. The circulation piping  88 B is connected to an individual piping  90 B in which an opening and closing valve  91 B and a flow rate adjusting valve  92 B are interposed. Downstream ends of the individual piping  90 A and the individual piping  90 B are connected to the sublimable substance-containing liquid piping  40  via a mixing valve  100 . 
     The solvent in the first diluting liquid tank  93 A is sent to a circulation piping  94 A by a pump  95 A and returns to the first diluting liquid tank  93 A from the circulation piping  88 A. The solvent in the second diluting liquid tank  93 B is sent to a circulation piping  94 B by a pump  95 B and returns to the second diluting liquid tank  93 B from the circulation piping  94 B. The circulation piping  94 A is connected to an individual piping  96 A in which an opening and closing valve  97 A and a flow rate adjusting valve  98 A are interposed. The circulation piping  94 B is connected to an individual piping  96 B in which an opening and closing valve  976  and a flow rate adjusting valve  98 B are interposed. Downstream ends of the individual piping  96 A and the individual piping  96 B are connected to the sublimable substance-containing liquid piping  40  via the mixing valve  100 . 
     The mixing valve  100  includes an individual flow passage  101 , an individual flow passage  102 , an individual flow passage  103 , and an individual flow passage  104  connected to the individual piping  90 A, the individual piping  90 B, the individual piping  96 A, and the individual piping  96 B, respectively. The mixing valve  100  further includes a first check valve V 1  that prevents backflow of liquid at the individual flow passage  101 , a second check valve V 2  that prevents backflow of liquid at the individual flow passage  102 , a third check valve V 3  that prevents backflow of liquid at the individual flow passage  103 , a fourth check valve V 4  that prevents backflow of liquid at the individual flow passage  104 , and a collecting flow passage  105  that is connected to downstream ends of the individual flow passage  101 , the individual flow passage  102 , the individual flow passage  103 , and the individual flow passage  104 . 
     Opening and closing of the opening and closing valve  91 A, the opening and closing valve  91 B, the opening and closing valve  97 A, and the opening and closing valve  976  and opening degrees of the flow rate adjusting valve  92 A, the flow rate adjusting valve  92 B, the flow rate adjusting valve  98 A, and the flow rate adjusting valve  98 B are controlled by the controller  3 . When the opening and closing valve  91 A is opened, the liquid containing the sublimable substance in the first undiluted liquid tank  87 A is supplied to the mixing valve  100  at a flow rate corresponding to the opening degree of the flow rate adjusting valve  92 A. The same applies when each of the opening and closing valve  91 B, the opening and closing valve  97 A, and the opening and closing valve  976  is opened. 
     At least one of the opening and closing valve  91 A and the opening and closing valve  91 B and at least one of the opening and closing valve  97 A and the opening and closing valve  976  are opened, the liquid, which contains the sublimable substance, and the solvent are supplied to the mixing valve  100  and mixed in the collecting flow passage  105  of the mixing valve  100 . Thus, the liquid containing the sublimable substance is diluted with the solvent, and the sublimable substance-containing liquid is manufactured. The sublimable substance-containing liquid manufactured in the mixing valve  100  is supplied to the sublimable substance-containing liquid nozzle  39  from the sublimable substance-containing liquid piping  40  and discharged from the sublimable substance-containing liquid nozzle  39  toward the upper surface of the substrate W. 
     In a case where the surface of the pattern P 1  is hydrophilic, the sublimable substance having the hydrophilic group and the solvent having less solubility in water than this sublimable substance are mixed in the mixing valve  100 . That is, the opening and closing valve  91 A, and the opening and closing valve  97 A or the opening and closing valve  976  are opened by the controller  3 . In a case where the surface of the pattern P 1  is hydrophobic, the sublimable substance having the hydrophobic group and the solvent having less solubility in oil than this sublimable substance are mixed in the mixing valve  100 . That is, the opening and closing valve  91 B, and the opening and closing valve  97 A or the opening and closing valve  976  are opened by the controller  3 . 
     When the sublimable substance-containing liquid is supplied to the substrate W, at least one of the opening and closing valve  91 A and the opening and closing valve  91 B and at least one of the opening and closing valve  97 A and the opening and closing valve  976  are opened. The plurality of valves to be opened may be specified in the recipe. In a case where information to determine whether the surface of the pattern P 1  hydrophilic and hydrophobic is input to the controller  3 , the controller  3  may select the plurality of valves to be opened. Such information includes, for example, information indicating material of the surface of the pattern P 1 , information indicating the type of liquid supplied to the substrate W before the sublimable substance-containing liquid is supplied, and so on. 
     It is noted that in a case where the liquid containing the sublimable substance contains a substance other than the sublimable substance (for example, the solvent), when at least one of the opening and closing valve  91 A and the opening and closing valve  91 B and at least one of the opening and closing valve  97 A and the opening and closing valve  976  are opened, the liquid containing the sublimable substance is diluted with the solvent. In this case, the substance other than the sublimable substance may be a solvent having the same name as that of the solvent for diluting, or may be a substance other than the solvent for diluting. In the latter case, when the liquid containing the sublimable substance is diluted with the solvent, the concentration of the substance other than the sublimable substance is lowered to a value where effects of this substance on the processing of the substrate W can be ignored. 
       FIG. 10  is a process chart for describing another example of the sublimable substance-containing liquid supplying step shown in  FIG. 6 . 
     In the substrate processing apparatus  1  according to the second preferred embodiment, as with the first preferred embodiment, each of the steps shown in  FIG. 6  is performed. 
     When the sublimable substance-containing liquid supplying step (step S 6  in  FIG. 6 ) is performed, the controller  3  determines whether or not the controller  3  should cause the sublimable substance-containing liquid nozzle  39  to discharge the sublimable substance-containing liquid (step S 21  in  FIG. 10 ). When there is no need to discharge (No in step S 21  in  FIG. 10 ), after a predetermined time elapsed, the controller  3  determines again whether or not the controller  3  should cause the sublimable substance-containing liquid to be discharged (return to step S 21  in  FIG. 10 ). 
     When there is need to discharge the sublimable substance-containing liquid (Yes in step S 21  in  FIG. 10 ), the controller  3  opens at least one of the opening and closing valve  91 A and the opening and closing valve  91 B and at least one of the opening and closing valve  97 A and the opening and closing valve  976  (step S 22  in  FIG. 10 ). Thus, the liquid containing the sublimable substance and the solvent are mixed, and the sublimable substance-containing liquid is manufactured in the mixing valve  100 . And the sublimable substance-containing liquid is discharged from the sublimable substance-containing liquid nozzle  39 . 
     After the discharging the sublimable substance-containing liquid is started, the controller  3  determines whether or not a predetermined time has elapsed (step S 23  in  FIG. 10 ). When the predetermined time has not elapsed (No in step S 23  in  FIG. 10 ), the controller  3  determines again whether or not the predetermined time has elapsed (return to step S 23  in  FIG. 10 ). When the predetermined time has elapsed (Yes in step S 23  in  FIG. 10 ), the controller  3  closes the plurality of valves that have been opened in step S 22  (step S 24  in  FIG. 10 ). Thus, the mixing of the liquid containing the sublimable substance and the solvent and the discharging the sublimable substance-containing liquid are stopped. 
     Other Preferred Embodiments 
     The present invention is not restricted to the contents of the above described preferred embodiments and various modifications are possible. 
     For example, in the first preferred embodiment, a tank for hydrophilicity that stores the sublimable substance-containing liquid for hydrophilicity to be supplied to the substrate W when the surface of the pattern P 1  is hydrophilic, and a tank for hydrophilicity that stores the sublimable substance-containing liquid for hydrophobicity to be supplied to the substrate W when the surface of the pattern P 1  is hydrophobic may be provided. 
     In this case, whether the surface of the pattern P 1  is hydrophilic or hydrophobic, it is possible to supply the appropriate sublimable substance-containing liquid and to lower the collapse rate of the pattern P 1 . Which of the sublimable substance-containing liquid for hydrophilicity and the sublimable substance-containing liquid for hydrophobicity is to be supplied to the substrate W may be specified in the recipe, or the controller  3  may select it based on information input in the controller  3 . 
     In the first preferred embodiment, the sublimable substance-containing liquid supplied from the undiluted liquid tank  87  may be mixed with the diluting liquid supplied from the diluting liquid tank  93  at a position other than the sublimable substance-containing liquid piping  40 . For example, the sublimable substance-containing liquid may be mixed with the diluting liquid at an inside or insides of at least one of piping other than the sublimable substance-containing liquid piping  40 , a valve such as the mixing valve  100 , and the sublimable substance-containing liquid nozzle  39 . The sublimable substance-containing liquid may be mixed with the diluting liquid at the upper surface of the substrate W. 
     Similarly, in the second preferred embodiment, the liquid containing the sublimable substance and supplied from at least one of the first undiluted liquid tank  87 A and the second undiluted liquid tank  876  may be mixed with the solvent supplied from at least one of the first diluting liquid tank  93 A and the second diluting liquid tank  93 B at a position other than the mixing valve  100 . For example, the liquid containing the sublimable substance may be mixed with the solvent at an inside or insides of at least one of a valve other than the mixing valve  100 , piping, and the sublimable substance-containing liquid nozzle  39 . The liquid containing the sublimable substance may be mixed with the solvent at the upper surface of the substrate W. The solid of the sublimable substance may be dissolved in the solvent at the inside of the cabinet CC. 
     The solidified film SF may be removed at the processing unit  2  different from the wet-processing unit  2 W. The processing unit  2  to remove the solidified film SF may be a portion of the substrate processing apparatus  1 , or may be a portion of a substrate processing apparatus different from the substrate processing apparatus  1 . That is, a single substrate processing system may include the substrate processing apparatus  1  including the wet-processing unit  2 W and a substrate processing apparatus including a processing unit  2  to remove the solidified film SF, and the substrate W may be transferred from the substrate processing apparatus  1  to another substrate processing apparatus before the solidified film SF is removed. 
     When the rinse liquid such as pure water on the substrate W can be replaced with the sublimable substance-containing liquid, the sublimable substance-containing liquid supplying step may be performed without performing the replacing liquid supplying step to replace the rinse liquid on the substrate W with the replacing liquid. 
     The shielding member  51  may rotate around the rotation axis A 1  together with the spin chuck  10 . For example, the shielding member  51  may be placed on the spin base  12  so as not to contact the substrate W. In the case, since the shielding member  51  is coupled to the spin base  12 , the shielding member  51  rotates at the same speed in the same direction as that of the spin base  12 . 
     The shielding member  51  may be eliminated. However, when a liquid such as pure water is supplied to the lower surface of the substrate W, the shielding member  51  is preferably provided. This is because the shielding member  51  can interrupt droplets flowing from the lower surface of the substrate W to the upper surface of the substrate W through the outer circumferential surface of the substrate W, or droplets that have bounced inwardly from the processing cup  21 , thus reducing a liquid that would be otherwise mixed into the sublimable substance-containing liquid on the substrate W. 
     The substrate processing apparatus  1  is not restricted to an apparatus for processing a disc-shaped substrate W, and may be an apparatus for processing a polygonal substrate W. 
     Two or more of all the arrangements described above may be combined. Two or more of all the steps described above may be combined. 
     The controller  3  is an example of the sublimable substance selecting unit and the solvent selecting unit. The sublimable substance-containing liquid supplying unit  99  is an example of the sublimable substance-containing liquid supplying unit. The spin chuck  10  and the central nozzle  55  are an example of the solidified film forming unit. The spin chuck  10  and the central nozzle  55  are also an example of the sublimating unit. The sublimable substance-containing liquid piping  40  and the mixing valve  100  are an example of the dissolving unit. 
     The preferred embodiments of the present invention are described in detail above, however, these are just detailed examples used for clarifying the technical contents of the present invention, and the present invention should not be limitedly interpreted to these detailed examples, and the spirit and scope of the present invention should be limited only by the claims appended hereto. 
     REFERENCE SIGNS LIST 
     
         
           1 : substrate processing apparatus 
           3 : controller (sublimable substance selecting unit, solvent selecting unit) 
           10  : spin chuck (solidified film forming unit, sublimating unit) 
           40  : sublimable substance-containing liquid piping (dissolving unit) 
           55  : central nozzle (solidified film forming unit, sublimating unit) 
           99  : sublimable substance-containing liquid supplying unit (sublimable substance-containing liquid supplying unit) 
           100  :mixing valve (dissolving unit) 
         P 1  : pattern 
         Ps : side surface of pattern 
         Px : upper end portion of side surface of pattern 
         SF : solidified film 
         W : substrate