Patent Publication Number: US-2022213382-A1

Title: Substrate processing device and etching liquid

Description:
CROSS-REFERENCE TO RELATED APPLICATION 
     This is a divisional application of U.S. Ser. No. 16/965,776, which is a U.S. national phase application under 35 U.S.C. § 371 of PCT Application No. PCT/JP2019/002141 filed on Jan. 23, 2019, which claims the benefit of Japanese Patent Application Nos. 2018-013985 and 2018-122609 filed on Jan. 30, 2018, and Jun. 28, 2018, the entire disclosures of which are incorporated herein by reference. 
    
    
     TECHNICAL FIELD 
     The various embodiments described herein pertain generally to a substrate processing method, a substrate processing device and an etching liquid. 
     BACKGROUND ART 
     Conventionally, in a manufacturing process of a semiconductor device, wet etching may be performed on a surface of a substrate such as a silicon wafer or a compound semiconductor wafer. 
     Patent Document 1: Japanese Patent No. 3,396,030 
     SUMMARY 
     In one exemplary embodiment, a substrate processing method includes holding a substrate; and supplying an etching liquid to the substrate held in the holding of the substrate, the etching liquid containing an etching agent configured to etch a metal-based first material and a silicon-based second material exposed on the substrate and a protection agent configured to react with the second material between the first material and the second material to form a protection layer on a surface of the second material, the etching agent being a liquid which contains fluorine atoms and an organic solvent and substantially does not contain water, and the protection layer protecting the second material from etching with the etching agent. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         FIG. 1  is a schematic diagram illustrating a configuration of a substrate processing system according to an exemplary embodiment. 
         FIG. 2  is a schematic view of a wafer according to the exemplary embodiment. 
         FIG. 3  is a schematic diagram illustrating a configuration of a substrate processing device according to the exemplary embodiment. 
         FIG. 4  is a table showing a relationship between solute and solvent combinations in an etching agent and an etchant. 
         FIG. 5  is a flowchart illustrating a sequence of processings performed by the substrate processing system according to the exemplary embodiment. 
         FIG. 6  is a diagram illustrating a configuration of a substrate processing device according to a first modification example. 
         FIG. 7  is a diagram illustrating a configuration of a substrate processing device according to a second modification example. 
         FIG. 8  is a diagram illustrating a configuration of a substrate processing device according to a third modification example. 
         FIG. 9  is a diagram illustrating a configuration of a substrate processing device according to a fourth modification example. 
         FIG. 10  is a diagram illustrating a configuration of a separation unit according to the fourth modification example. 
         FIG. 11  is a flowchart illustrating a sequence of processings performed by the substrate processing system according to the fourth modification example. 
         FIG. 12  is a diagram illustrating a configuration of a separation unit according to a fifth modification example. 
     
    
    
     DETAILED DESCRIPTION 
     Hereinafter, embodiments (hereinafter, referred to as “exemplary embodiments”) of a substrate processing method, a substrate processing device and an etching liquid according to the present disclosure will be described in detail with reference to the accompanying drawings. Further, the substrate processing method, the substrate processing device and the etching liquid of the present application are not limited to the following exemplary embodiments. Furthermore, the exemplary embodiments can be appropriately combined as long as processing contents are not contradictory to each other. Also, in each of the exemplary embodiments described below, same parts will be assigned same reference numerals, and redundant description will be omitted. 
     Patent Document 1 discloses a technique of adjusting an etching rate of a gate oxide film to be equal to or smaller than 10 Å/min by using, as an etching liquid, an ammonium fluoride solution in which ammonium fluoride is dissolved in a low dielectric constant solvent, e.g., acetic acid or tetrahydrofuran. According to this technique, it is possible to remove metal-based sub-products formed on side walls of a gate electrode while suppressing the gate oxide film from being etched. 
     However, according to the technique described in Patent Document 1, a material, e.g., a silicon oxide film, which needs to be left on a substrate as well as the metal-based sub-products can be removed by the ammonium fluoride solution. Therefore, a technique capable of improving the selectivity of wet etching has been expected. 
     &lt;1. Configuration of Substrate Processing System&gt; 
     First, a configuration of a substrate processing system according to an exemplary embodiment will be described.  FIG. 1  is a schematic diagram illustrating the configuration of the substrate processing system according to the exemplary embodiment. Also,  FIG. 2  is a schematic view of a wafer according to the exemplary embodiment. Further, in the following, in order to clarify positional relationships, the X-axis, the Y-axis, and the Z-axis which are orthogonal to each other will be defined. The positive Z-axis direction will be regarded as a vertically upward direction. 
     As illustrated in  FIG. 1 , a substrate processing system  1  includes a carry-in/out station  2  and a processing station  3 . The carry-in/out station  2  and the processing station  3  are provided adjacent to each other. 
     The carry-in/out station  2  is equipped with a carrier placing section  11  and a transfer section  12 . In the carrier placing section  11 , a plurality of transfer containers (hereinafter, referred as “carriers C”) is placed to accommodate a plurality of wafers W horizontally. 
     The transfer section  12  is provided adjacent to the carrier placing section  11 . The transfer section  12  is equipped with a substrate transfer device  121  and a delivery unit  122  therein. 
     The substrate transfer device  121  is equipped with a wafer holding mechanism configured to hold a wafer W. Further, the substrate transfer device  121  is movable horizontally and vertically and pivotable around a vertical axis. The substrate transfer device  121  transfers the wafer W between the carrier C and the delivery unit  122  by the wafer holding mechanism. 
     The processing station  3  is provided adjacent to the transfer section  12 . The processing station  3  is equipped with a transfer section  13  and a plurality of substrate processing devices  14 . The plurality of substrate processing devices  14  may be arranged on both sides of the transfer section  13 . 
     The transfer section  13  is equipped with a substrate transfer device  131  therein. The substrate transfer device  131  is equipped with a wafer holding mechanism configured to hold the wafer W. Further, the substrate transfer device  131  is movable horizontally and vertically and pivotable around a vertical axis. The substrate transfer device  131  transfers the wafer W between the delivery unit  122  and the substrate processing device  14  by the wafer holding mechanism. 
     The substrate processing device  14  performs a wet etching processing (hereinafter, simply referred to as “etching processing”). The etching processing is performed to remove a reaction product generated during, for example, dry etching. Further, the etching processing may be performed to remove a material, such as copper, which is difficult to remove by the dry etching. 
     As illustrated in  FIG. 2 , the wafer W according to the exemplary embodiment is a silicon wafer, a compound semiconductor wafer or the like, and a first material  101 , which is an etching target, and a second material  102 , which is a non-etching target, are exposed on a surface of the wafer W. 
     The first material  101  is composed of a metal-based material. The metal-based material may include a metal, a metal oxide, and other metal-containing materials. 
     For example, the first material  101  is a metal-based reaction product generated by the dry etching. Although  FIG. 2  illustrates an example where the first material  101  adheres to an upper portion of a pattern, the first material  101  may adhere to any place other than the upper portion of the pattern. For example, the first material  101  may adhere on the second material  102 . 
     The second material  102  is composed of a silicon-based material. For example, the second material  102  is a silicon-based film such as a silicon oxide film, a silicon thermal oxide film, a silicon nitride film, a silicon oxynitride film or the like. Although  FIG. 2  illustrates an example where the second material  102  is exposed on a bottom surface of a recess of the pattern, the second material  102  may be exposed on any place other than the bottom surface of the recess of the pattern. 
     The first material  101  can be removed with a fluorine-based etching liquid such as a hydrogen fluoride solution, an ammonium fluoride solution or an ammonium hydrogen fluoride solution. However, the fluorine-based etching liquid can also remove the second material  102  which is composed of the silicon-based material. 
     Therefore, the substrate processing device  14  according to the exemplary embodiment of the present disclosure performs the etching processing on the wafer W with an etching liquid prepared by adding a protection agent, which reacts with the second material  102  but does not react with the first material  101 , into a fluorine-based etching agent. The composition of the etching liquid will be described in detail later. 
     The substrate processing system  1  is equipped with a control device  4 . The control device  4  controls the operations of the substrate processing system  1 . The control device  4  is, for example, a computer and includes a controller  15  and a storage  16 . The storage  16  stores programs that control various processings such as etching processing. The controller  15  controls the operations of the substrate processing system  1  by reading and executing the program stored in the storage  16 . The controller  15  is, for example, a central processing unit (CPU) or a microprocessor unit (MPU), and the storage  16  is, for example, a read only memory (ROM) or a random access memory (RAM). 
     Further, the program may be stored in a computer-readable recording medium, and installed from the recording medium to the storage  16  of the control device  4 . The computer-readable recording medium may be, for example, a hard disc (HD), a flexible disc (FD), a compact disc (CD), a magnet optical disc (MO), or a memory card. 
     In the substrate processing system  1  configured as described above, the substrate transfer device  121  of the carry-in/out station  2  first takes out the wafer W from the carrier C and then places the taken wafer Won the delivery unit  122 . The wafer W placed on the delivery unit  122  is taken out from the delivery unit  122  by the substrate transfer device  131  of the processing station  3  and carried into the substrate processing device  14 . The wafer W carried into the substrate processing device  14  is etched by the substrate processing device  14  and then carried out from the substrate processing device  14  to be placed on the delivery unit  122  by the substrate transfer device  131 . Thereafter, the wafer W is returned to the carrier C by the substrate transfer device  121 . 
     &lt;2. Configuration of Substrate Processing Device&gt; 
     Hereinafter, the configuration of the substrate processing device  14  will be described with reference to  FIG. 3 .  FIG. 3  is a schematic diagram illustrating the configuration of the substrate processing device  14  according to the exemplary embodiment. 
     As illustrated in  FIG. 3 , the substrate processing device  14  is equipped with a chamber  20 , a substrate holding mechanism  30 , a liquid supply  40  and a recovery cup  50 . 
     The chamber  20  accommodates therein the substrate holding mechanism  30 , the liquid supply  40  and the recovery cup  50 . A fan filter unit (FFU)  21  is provided on a ceiling portion of the chamber  20 . The FFU  21  forms a downflow inside the chamber  20 . 
     The FFU  21  is connected to a downflow gas source  23  via a valve  22 . The FFU  21  discharges a downflow gas (for example, dry air) supplied from the downflow gas source  23  into the chamber  20 . 
     The substrate holding mechanism  30  is equipped with a rotation holder  31 , a support  32  and a driver  33 . The rotation holder  31  is provided in an approximately central part of the chamber  20 . On the rotation holder  31 , holding members  311  configured to hold the wafer W from the side thereof are provided. The wafer W is held horizontally by the holding members  311  above the rotation holder  31  with a small space from the rotation holder  31 . 
     The support  32  is a member extending vertically. A base end portion of the support  32  is rotatably supported by the driver  33  and a tip end portion of the support  32  supports the rotation holder  31  horizontally. The driver  33  rotates the support  32  around a vertical axis. 
     By rotating the support  32  with the driver  33 , the substrate holding mechanism  30  rotates the rotation holder  31  supported by the support  32  and thus rotates the wafer W held by the rotation holder  31 . 
     Further, the rotation holder  31  has a type of holding the wafer W from the side thereof, but is not limited thereto. For example, the rotation holder  31  may suck and hold the wafer W from its bottom side like a vacuum chuck. 
     The liquid supply  40  is configured to supply various processing liquids to the wafer W held by the substrate holding mechanism  30 . The liquid supply  40  is equipped with a plurality of (herein, two) nozzles  41   a  and  41   b , an arm  42  configured to hold the nozzles  41   a  and  41   b  horizontally and a pivotable elevation mechanism  43  configured to pivot and elevate the arm  42 . The nozzle  41   a  and the nozzle  41   b  may be supported by different arms, respectively. 
     The nozzle  41   a  is connected to an etching liquid source  45   a  via a valve  44   a  and a flow rate controller  46   a . Also, the nozzle  41   b  is connected to a rinse liquid source  45   b  via a valve  44   b  and a flow rate controller  46   b.    
     An etching liquid supplied from the etching liquid source  45   a  is discharged from the nozzle  41   a . Details of the etching liquid will be described later. 
     A rinse liquid supplied from the rinse liquid source  45   b  is discharged from the nozzle  41   b . The rinse liquid is, for example, deionized water (DIW). 
     The recovery cup  50  is disposed to surround the rotation holder  31  and collects the processing liquid scattered from the wafer W by the rotation of the rotation holder  31 . A drain port  51  is formed on a bottom of the recovery cup  50 , and the processing liquid collected by the recovery cup  50  is drained from the drain port  51  to the outside of the substrate processing device  14 . Further, an exhaust port  52  is formed on the bottom of the recovery cup  50  to discharge the downflow gas supplied from the FFU  21  to the outside of substrate processing device  14 . 
     Furthermore, the number of nozzles provided in the substrate processing device  14  is not limited to the above-described example. For example, the substrate processing device  14  may be equipped with a single nozzle for discharging the etching liquid and the rinse liquid. 
     &lt;3. Etching Liquid&gt; 
     The etching liquid according to the exemplary embodiment contains an “etching agent” and a “protection agent”. 
     The “etching agent” is a fluorine-based chemical liquid configured to etch the first material  101 , which is an etching target, among a plurality of materials exposed on the wafer W. However, the “etching agent” is also configured to etch the second material  102 , which is a non-etching target, as well as the first material  101 . 
     Therefore, the etching liquid according to the exemplary embodiment contains “protection agent”. The “protection agent” is a chemical which reacts with the second material  102  between the first material  101  and the second material  102  to form a protection layer on the surface of the second material  102 . With the etching liquid according to the exemplary embodiment, the protection agent can protect the surface of the second material  102 , and, thus, it is possible to suppress etching of the second material  102  with the etching agent while etching the first material  101 . Therefore, with the etching liquid according to the exemplary embodiment, it is possible to improve the selectivity between the first material  101  and the second material  102 . 
     Hereinafter, the “etching agent” and the “protection agent” contained in the etching liquid according to the exemplary embodiment will be described in detail. 
     &lt;3-1. Etching Agent&gt; 
     The etching agent according to the exemplary embodiment is a liquid which contains fluorine atoms and an organic solvent and substantially does not contain water. The etching agent used herein may be a solution containing any one of hydrogen fluoride (HF), ammonium hydrogen fluoride (NH 4 HF 2 ), and ammonium fluoride (NH 4 F) as a solute and any one of isopropyl alcohol (IPA), methanol and ethanol as a solvent. 
     The solute just needs to be a material containing at least a fluorine atom and is not limited to HF, NH 4 HF 2  and NH 4 F. Also, the solvent just needs to be an organic solvent and is not limited to IPA, methanol and ethanol. 
     Further, the term “substantially does not contain water” means that water is not actively contained but water which is inevitably mixed such as a minute amount of water contained in a solute or a solvent is allowed. Specifically, the term “substantially does not contain water” means that water is not contained at all or if water is contained, the content of water is equal to “1.0 wt % or less”. 
       FIG. 4  is a table showing the relationship between combinations of the solute and the solvent in the etching agent and an etchant.  FIG. 4  shows six types of etching agents. Specifically, there are three types of etching agents containing HF, NH 4 F and NH 4 HF 2 , respectively, as the solute and H 2 O as the solvent, and there are other three types of etching agents containing HF, NH 4 F and NH 4 HF 2 , respectively, as the solute and isopropyl alcohol (IPA) as the solvent. In  FIG. 4 , “(50%)” indicates that the concentration is 50%, and “(s)” indicates a saturated aqueous solution. Also, in  FIG. 4 , the amount of the etchant is expressed in three levels as “Rich”, “Avg” and “Poor” in this order from the largest. 
     As shown in  FIG. 4 , it can be seen that when water (H 2 O) is used as the solvent, a plurality of types of etchants, specifically HF, H + , F −  and HF 2   − , exists in each etching agent. This is because water has a high relative dielectric constant and undergoes various ionizations (first ionization, second ionization, etc.) due to chemical equilibrium, resulting in an equilibrium state. The plurality of types of etchants may include not only an etchant which etches the etching target but also an etchant which etches the non-etching target. Therefore, it is difficult to perform selective etching. 
     Also, it can be seen that when IPA is used as the solvent, only HF exists as the etchant for the etching agent containing HF as the solute and only H +  and F −  exist for NH 4 F and only HF 2   −  exists for NH 4 HF 2 . This is because IPA has a lower relative dielectric constant than water, and, thus, ionization of ammonium hydrogen fluoride (NH 4 HF 2 ) or ammonium fluoride (NH 4 F) is suppressed. For example, in the etching agent containing HF as the solute and IPA as the solvent, H +  or F −  cannot exist but only HF, which is a neutral molecule, exists in IPA. 
     Combinations of the solute and the solvent can be appropriately selected according to the etching target. For example, in the etching agent containing NH 4 HF 2  as the solute and methanol as the solvent, only first ionization occurs, and, thus, and only HF 2   − , which is an etchant of SiO 2 , can be generated. As a result, for example, a thermal oxide film known to be dense and have a low etching rate can be etched at a higher etching rate than aluminum oxide (AlO). Further, in the etching agent containing NH 4 F as the solute and methanol as the solvent, only the first ionization occurs, and, thus, HF 2   − , which is an etchant of SiO 2 , is not generated. Therefore, it is possible to suppress etching of SiO 2 . 
     Desirably, a material having a relative dielectric constant of 40 or less is used as the organic solvent. The relative dielectric constant of methanol is 32.7, the relative dielectric constant of ethanol is 26.4, and the relative dielectric constant of IPA is 19.9. The etching agent can be obtained by dissolving a salt such as NH 4 HF 2  or NH 4 F in the organic solvent. The etching agent is not limited to salt and can be obtained by dissolving, for example, an HF gas in the organic solvent. 
     As described above, by using the organic solvent which substantially does not contain water having a high relative dielectric constant and has a lower relative dielectric constant than water, the type of etchant can be limited. Thus, the etching selectivity can be improved. The etching liquid according to the exemplary embodiment further contains the protection agent and thus further improves the etching selectivity. 
     &lt;3-2. Protection Agent&gt; 
     The protection agent is a chemical which reacts with the silicon-based material to form the protection layer on the surface of the silicon-based material. For example, a silylating agent may be used as the protection agent. The silylating agent is configured to react with and adsorb an Si-containing dielectric material or an Si surface. 
     Specifically, the protection agent is a chemical represented by the following Chemical Formula 1: 
     
       
         
         
             
             
         
       
     
     In the above Chemical Formula 1, R 1  to R 5  each independently represents an alkyl group substituted with a halogen or an unsubstituted alkyl group. The alkyl group is, for example, an alkyl group having a carbon number of 1 to 8. Examples of the protection agent having the structure represented by Chemical Formula 1 include trimethylsilyl dimethylamine (TMSDMA) and butyldimethylsilyl dimethylamine (BDMSDMA). Also, examples of the protection agent having the structure represented by Chemical Formula 1 include triethylsilyl dimethylamine (TESDMA) and nanofluorohexyl dimethyl(dimethylamine)silane (NFHDMA). 
     Also, the protection agent may be a chemical represented by the following Chemical Formula 2: 
     
       
         
         
             
             
         
       
     
     In the above Chemical Formula 2, R 6  to R 12  each independently represents an alkyl group or a hydrogen atom. The alkyl group is, for example, an alkyl group having a carbon number of 1 to 8. Examples of the protection agent having the structure represented by Chemical Formula 2 include hexamethyldisilazane (HMDS). 
     Further, the protection agent may be a chemical represented by the following Chemical Formula 3: 
     
       
         
         
             
             
         
       
     
     In the above Chemical Formula 3, R 13  to R 19  each independently represents an alkyl group. The alkyl group is, for example, an alkyl group having a carbon number of 1 to 8. Examples of the protection agent having the structure represented by Chemical Formula 3 include N, N-dimethylamino pentamethyldisilane (DMAPMDS). 
     All of these protection agents having the structures represented by Chemical Formulas 1 to 3 have a direct bond between a silicon atom and a nitrogen atom. The direct bond between the silicon atom and the nitrogen atom is broken in the organic solvent as the solvent and then separated into a silicon atom-side molecule and a nitrogen atom-side molecule. Then, the silicon atom-side molecule (e.g., as for TMSDMA, trimethylsilane (—Si(CH 3 ) 3 )) is adsorbed on the surface of the silicon-based material, i.e., is bonded to the silicon atom present on the surface of the silicon-based material. Thus, a dangling bond of the silicon atom present on the surface of the silicon-based material is filled, so that an etchant (e.g., HF 2   − ) of the silicon-based material is hardly adsorbed. Therefore, the etching of the silicon-based material with the etching agent can be suppressed. 
     In addition, some chemicals that do not have the direct bond between the silicon atom and the nitrogen atom, such as a silane coupling agent, may be adsorbed on the surface of the silicon-based material. However, for example, if the a silane coupling agent is used as the protection agent, the silane coupling agent needs to be bonded to water in order to generate molecules that are adsorbed on the surface of the silicon-based material. For this reason, if the silane coupling agent is applied to the etching liquid which substantially does not contain water, for example, a drying process is needed. Meanwhile, since the direct bond between the silicon atom and the nitrogen atom is broken in the organic solvent, it is suitable for the application to the etching liquid which substantially does not contain water. 
     In addition, the protection agent, which is the silylating agent, reacts with the silicon-based material but hardly reacts with the metal-based material. In this regard, the present inventors conducted an experiment in which TMSDMA, which is the silylating agent, is supplied to the metal-based material and the silicon-based material and a change in contact angle before and after the supply of TMSDMA is examined. Examples of the metal-based material include Al, Co, CoPt, Cu, Al 2 O 3  and the like. Also, examples of the silicon-based material include bare silicon, a thermal oxide film, SiON, SiN, spin-on glass, an interlayer insulating film and the like. As a result, it is observed that as for the silicon-based material, the contact angle is changed greatly after the supply of TMSDMA (increased to 90° or more in all the silicon-based materials), whereas as for the metal-based material, the contact angle is changed rarely. It can be seen from this result that the protection agent, which is the silylating agent, reacts with the silicon-based material but hardly reacts with the metal-based material. 
     As such, by using the silylating agent as the protection agent, the etching of the silicon-based material can be suppressed without inhibiting the etching of the metal-based material. Therefore, the etching liquid according to the exemplary embodiment can be appropriately used to etch the metal-based material but not to etch the silicon-based material on the substrate where the metal-based material (first material  101 ) and the silicon-based material (second material  102 ) are exposed on the surface. 
     In addition, when the content of the protection agent is too high, the etching rate of the metal-based material, which is the etching target, may decrease. For this reason, the molar content of the protection agent in the etching liquid is desirably 5.0 times or less and more desirably 3.0 times or less than that of the etching agent. 
     &lt;4. Specific Operations of Substrate Processing System&gt; 
     Hereinafter, specific operations of the substrate processing device  14  will be described with reference to  FIG. 5 .  FIG. 5  is a flowchart illustrating a sequence of processings performed by the substrate processing system  1  according to the exemplary embodiment. The devices included in the substrate processing system  1  perform the respective processings according to the sequence illustrated in  FIG. 5  under the control of the controller  15 . 
     As illustrated in  FIG. 5 , in the substrate processing device  14 , a substrate carry-in processing is performed first (process S 101 ). In the substrate carry-in processing, the wafer W carried into the chamber  20  by the substrate transfer device  131  (see  FIG. 1 ) is held by the holding member  311  of the substrate holding mechanism  30 . The wafer W is held by the holding member  311  with the pattern forming surface thereof facing upwards. Thereafter, the rotation holder  31  is rotated by the driver  33 . Thus, the wafer W rotates together with the rotation holder  31  while being held horizontally by the rotation holder  31 . The rotation number of the wafer W is set to a first rotation number. 
     Then, the substrate processing device  14  performs an etching processing with the above-described etching liquid (process S 102 ). In the etching processing, the nozzle  41   a  of the liquid supply  40  is located above the center of the wafer W. Thereafter, the valve  44   a  is opened for a predetermined time period and the etching liquid is supplied to the pattern forming surface of the wafer W. 
     The etching liquid supplied to the wafer W spreads on the surface of the wafer W due to a centrifugal force caused by the rotation of the wafer W. Thus, the first material  101  (see  FIG. 2 ) exposed on the surface of the wafer W is etched with the etching agent contained in the etching liquid. Further, the protection agent contained in the etching liquid reacts with the second material  102  to form the protection layer on the surface of the second material  102 , and, thus, it is possible to suppress the etching of the second material  102  with the etching agent. Therefore, it is possible to etch the first material  101 , which is the etching target, while suppressing the etching of the second material  102 , which is the non-etching target. 
     Subsequently, the substrate processing device  14  performs a rinse processing (process S 103 ). In the rinse processing, the nozzle  41   b  of the liquid supply  40  is located above the center of the wafer W. Thereafter, a valve  44   c  is opened for a predetermined time period and DIW, which is the rinse liquid, is supplied to the wafer W. The DIW supplied to the wafer W spreads on the pattern forming surface of the wafer W due to the centrifugal force caused by the rotation of the wafer W. As a result, the etching liquid remaining on the wafer W is washed away by the DIW. 
     Subsequently, the substrate processing device  14  performs a dry processing (process S 104 ). In the dry processing, for example, by increasing the rotation number of the wafer W from the first rotation number to a second rotation number, the DIW remaining on the surface of the wafer W is shaken off to dry the wafer W. 
     Then, the substrate processing device  14  performs a substrate carry-out processing (process S 105 ). In the substrate carry-out processing, the wafer W is taken out from the chamber  20  of the substrate processing device  14  by the substrate transfer device  131  (see  FIG. 1 ). Thereafter, the wafer W is accommodated in the carrier C placed on the carrier placing section  11  via the delivery unit  122  and the substrate transfer device  121 . When the substrate carry-out processing is completed, the processing for one wafer W is completed. 
     As described above, the substrate processing device  14  according to the exemplary embodiment includes the substrate holding mechanism  30  (an example of a holder) and the liquid supply  40  (an example of a supply). The substrate holding mechanism  30  holds the wafer W (an example of a substrate). The liquid supply  40  supplies the etching liquid to the wafer W held by the substrate holding mechanism  30 . The etching liquid contains the etching agent which etches the metal-based first material  101  and the silicon-based second material  102  exposed on the wafer W; and the protection agent which reacts with the second material  102  between the first material  101  and the second material  102  to form the protection layer on the surface of the second material  102 . The etching agent is the liquid which contains fluorine atoms and the organic solvent and substantially does not contain water. The protection layer protects the second material from etching with the etching agent. 
     Therefore, the substrate processing device  14  according to the exemplary embodiment can improve the selectivity of the wet etching. 
     &lt;5. Modification Examples&gt; 
     (First Modification Example) 
     In the above-described exemplary embodiment, there has been described the example where the etching liquid in which the etching agent and the protection agent are previously mixed is supplied to the liquid supply  40 . However, the etching agent and the protection agent may be mixed immediately before being supplied to the wafer W. Thus, it is possible to suppress the degradation of the etching liquid which occurs after the etching agent and the protection agent are reacted with each other. 
       FIG. 6  is a diagram illustrating a configuration of a substrate processing device according to a first modification example. In  FIG. 6 , the configuration of the rinse liquid supply system is appropriately omitted. Also, in the following description, the same components as described above will be denoted by like reference numerals and redundant descriptions thereof will be omitted. 
     As illustrated in  FIG. 6 , an etching liquid supply system  450 A according to the first modification example includes an etching agent source  451 , a first valve  452 , a first flow rate controller  453 , a protection agent source  454 , a second valve  455  and a second flow rate controller  456 . 
     Also, a substrate processing device  14 A according to the first modification example includes a mixing unit  160 . The mixing unit  160  is configured to generate the etching liquid by mixing the etching agent supplied from the etching agent source  451  at a predetermined flow rate with the protection agent supplied from the protection agent source  454  at a predetermined flow rate at a predetermined mixing ratio while maintaining the flow rates. 
     The mixing unit  160  is placed inside the chamber  20  (see  FIG. 3 ) of the substrate processing device  14 A. For example, the mixing unit  160  may be provided on the arm  42  of a liquid supply  40 A. 
     In the etching processing according to the first modification example, the first valve  452  is opened for a predetermined time period and the second valve  455  is opened for a predetermined time period. Thus, the etching agent and the protection agent are supplied into the mixing unit  160  while maintaining the flow rates thereof to be mixed in the mixing unit  160 . The mixing ratio between the etching agent and the protection agent is adjusted to a predetermined mixing ratio by the first flow rate controller  453  and the second flow rate controller  456 . 
     Thereafter, the etching liquid generated in the mixing unit  160  is discharged from the nozzle  41   a  onto the surface of the wafer W. The etching liquid discharged onto the surface of the wafer W spreads on the wafer W due to the centrifugal force caused by the rotation of the wafer W. Thus, the first material  101  exposed on the surface of the wafer W is etched. 
     As described above, the substrate processing device  14 A may mix the etching agent supplied from the etching agent source  451  and the protection agent supplied from the protection agent source  454  while maintaining the flow rates thereof. 
     (Second Modification Example) 
     The etching agent and the protection agent may be mixed on the wafer W.  FIG. 7  is a diagram illustrating a configuration of a substrate processing device according to a second modification example. In  FIG. 7 , the configuration of the rinse liquid supply system is appropriately omitted, as in  FIG. 6 . 
     As illustrated in  FIG. 7 , an etching liquid supply system  450 B according to the second modification example includes the etching agent source  451 , the first valve  452 , the first flow rate controller  453 , the protection agent source  454 , the second valve  455  and the second flow rate controller  456 . 
     Also, a substrate processing device  14 B according to the second modification example includes a liquid supply  40 B. The liquid supply  40 B includes a first nozzle  41   a   1  and a second nozzle  41   a   2 . The first nozzle  41   a   1  is connected to the etching agent source  451  via the first valve  452  and the first flow rate controller  453 , and discharges the etching agent supplied from the etching agent source  451  to the wafer W. The second nozzle  41   a   2  is connected to the protection agent source  454  via the second valve  455  and the second flow rate controller  456 , and discharges the protection agent supplied from the protection agent source  454  to the wafer W. 
     In the etching processing according to the second modification example, the first valve  452  is opened for a predetermined time period and the second valve  455  is opened for a predetermined time period. Thus, the etching agent is supplied from the etching agent source  451  to the first nozzle  41   a   1 , and the protection agent is supplied from the protection agent source  454  to the second nozzle  41   a   2 . Then, the etching agent is discharged from the first nozzle  41   a   1  onto the surface of the wafer W, and the protection agent is discharged from the second nozzle  41   a   2  onto the surface of the wafer W. As a result, the etching agent and the protection agent are mixed on the wafer W to generate the etching liquid. The generated etching liquid spreads on the wafer W due to the centrifugal force caused by the rotation of the wafer W. Thus, the first material  101  exposed on the surface of the wafer W is etched. 
     As described above, the etching agent and the protection agent may be mixed on the wafer W. Herein, there has been described an example where the etching agent and the protection agent are simultaneously supplied onto the wafer W, but either the etching agent or the protection agent may be supplied to the wafer W earlier than the other. 
     (Third Modification Example) 
     In the above-described exemplary embodiment and medication examples, there has been described the example the etching liquid is used in a single-wafer type etching. However, the etching liquid may be used in a batch type etching for collectively processing a plurality of wafers W. Hereinafter, an example of a substrate processing device configured to perform the batch type etching will be described with reference to  FIG. 8 .  FIG. 8  is a diagram illustrating a configuration of a substrate processing device according to a third modification example. 
     As illustrated in  FIG. 8 , an etching liquid supply system  450 C according to the third modification example includes an etching liquid source  457 , a valve  458  and a flow rate controller  459 . 
     Also, a substrate processing device  14 C according to the third modification example includes a processing tank  90 , a substrate holding mechanism  30 C and a liquid supply  40 C. 
     The processing tank  90  stores an etching liquid therein. The substrate holding mechanism  30 C collectively holds a plurality of wafers W in a vertical posture. The substrate holding mechanism  30 C can be moved up and down by a non-illustrated elevation mechanism. The liquid supply  40 C is connected to the etching liquid source  457  via the valve  458  and the flow rate controller  459 , and is configured to supply the etching liquid into the processing tank  90 . As a result, the processing tank  90  stores the etching liquid therein. 
     In the etching processing according to the third modification example, the substrate holding mechanism  30 C is moved down to immerse the plurality of wafers W held by the substrate holding mechanism  30 C in the etching liquid stored in the processing tank  90 . Thus, the first material  101  exposed on the surfaces of the wafers W is etched. 
     As described above, the etching liquid can also be applied to the batch type etching for collectively processing the wafers W. 
     (Fourth Modification Example) 
     Hereinafter, a configuration of a substrate processing device according to a fourth modification example will be described with reference to  FIG. 9 .  FIG. 9  is a diagram illustrating the configuration of the substrate processing device according to the fourth modification example. 
     As illustrated in  FIG. 9 , a substrate processing device  14 D according to the fourth modification example includes a liquid supply  40 D. The liquid supply  40 D includes nozzles  41   a  to  41   c , an arm  42  configured to hold the nozzles  41   a  to  41   c  horizontally and a pivotable elevation mechanism  43  configured to pivot and elevate the arm  42 . 
     The nozzle  41   a  is connected to the etching liquid source  45   a , and the valve  44   a  and the flow rate controller  46   a  are provided between the etching liquid source  45   a  and the nozzle  41   a . Also, the nozzle  41   b  is connected to the rinse liquid source  45   b , and the valve  44   b  and the flow rate controller  46   b  are provided between the rinse liquid source  45   b  and the nozzle  41   b . Further, the nozzle  41   c  is connected to an organic processing liquid source  45   c , and the valve  44   c  and a flow rate controller  46   c  are provided between the organic processing liquid source  45   c  and the nozzle  41   c.    
     The organic processing liquid source  45   c  is configured to supply an organic solvent to be contained in the etching agent of the etching liquid. The organic solvent supplied from the organic processing liquid source  45   c  is used in a line cleaning processing and a dry processing which will be described later. 
     In the fourth modification example, an organic solvent having a lower boiling point than water is used. Examples of the organic solvent may include ethanol, methanol, IPA, and the like. 
     First and second rotary cups  111  and  112  configured to rotate integrally with the rotation holder  31  are provided at a peripheral portion of the rotation holder  31 . As illustrated in  FIG. 9 , the second rotary cup  112  is placed inside the first rotary cup  111 . 
     Each of the first rotary cup  111  and the second rotary cup  112  is formed into a ring shape as a whole. The first and second rotary cups  111  and  112  rotate together with the rotation holder  31  and guide the processing liquid scattered from the wafer W being rotated to the recovery cup  50 . 
     The recovery cup  50  includes a first cup  50   a , a second cup  50   b  and a third cup  50   c  in this order from the inner side near the rotation center of the wafer W. Further, the recovery cup  50  includes a cylindrical inner wall member  54   d  centering on the rotation center of the wafer W at an inner circumferential side of the first cup  50   a.    
     The first to third cups  50   a  to  50   c  and the inner wall member  54   d  are provided on a bottom portion  53  of the recovery cup  50 . 
     The first cup  50   a  includes a first circumferential wall member  54   a  and a first liquid receiving member  55   a . The first circumferential wall member  54   a  stands up from the bottom portion  53  and is formed into a barrel shape (for example, a cylindrical shape). A space is formed between the first circumferential wall member  54   a  and the inner wall member  54   d , and this space serves as a first drain groove  501  for recovering and discharging the processing liquid and the like. The first liquid receiving member  55   a  is provided above an upper surface of the first circumferential wall member  54   a.    
     The first cup  50   a  includes a first elevation mechanism  56  and is configured to be movable up and down by the first elevation mechanism  56 . The first elevation mechanism  56  includes, for example, a support member which extends in a vertical direction and supports the first liquid receiving member  55   a ; and a driver configured to elevate the support member along the vertical direction. The driver is controlled by the control device  4 . Therefore, the first liquid receiving member  55   a  is moved between a processing position where the first liquid receiving member  55   a  receives the processing liquid scattered from the wafer W being rotated and a retreat position retreated downwards from the processing position. 
     When the first liquid receiving member  55   a  is at the processing position, an opening is formed at an inner side of an upper end of the first liquid receiving member  55   a  and a flow path leading from the opening to the first drain groove  501  is formed. Also, as illustrated in  FIG. 9 , the inner wall member  54   d  includes an extended portion  54   d   1  which extends so as to be incline toward the peripheral portion of the rotation holder  31 . When the first liquid receiving member  55   a  is at the retreat position, the first liquid receiving member  55   a  is in contact with the extended portion  54   d   1  of the inner wall member  54   d . Thus, the opening at the inner side of the upper end is closed, so that the flow path leading to the first drain groove  501  is blocked. 
     The second cup  50   b  includes a second circumferential wall member  54   b , a second liquid receiving member  55   b  and a second elevation mechanism  57 , and is placed adjacent to the first circumferential wall member  54   a  of the first cup  50   a.    
     The second circumferential wall member  54   b  stands up from the bottom portion  53  at an outer circumferential side of the first circumferential wall member  54   a  to be formed into a cylindrical shape. A space formed between the second circumferential wall member  54   b  and the first circumferential wall member  54   a  serves as a second drain groove  502  for recovering and discharging the processing liquid and the like. 
     The second liquid receiving member  55   b  is located at an outer circumferential side of the first liquid receiving member  55   a  and disposed above an upper surface of the second circumferential wall member  54   b . The second elevation mechanism  57  includes, for example, a support member which extends in the vertical direction and supports the second liquid receiving member  55   b ; and a driver configured to elevate the support member along the vertical direction. The driver is controlled by the control device  4 . Therefore, the second liquid receiving member  55   b  is moved between a processing position where the second liquid receiving member  55   b  receives the processing liquid scattered from the wafer W being rotated and a retreat position retreated downwards from the processing position. 
     When the second liquid receiving member  55   b  is at the processing position and the first liquid receiving member  55   a  is at the retreat position, an opening is formed at an inner side of an upper end of the second liquid receiving member  55   b  and a flow path leading from the opening to the second drain groove  502  is formed. Also, as illustrated in  FIG. 9 , when the second liquid receiving member  55   b  is at the retreat position, the second liquid receiving member  55   b  is in contact with the first liquid receiving member  55   a . Thus, the opening at the inner side of the upper end is closed, so that the flow path leading to the second drain groove  502  is blocked. In the above description, the second liquid receiving member  55   b  at the retreat position is in contact with the first liquid receiving member  55   a , but is not limited thereto. For example, the second liquid receiving member  55   b  may be in contact with the inner wall member  54   d  to close the opening at the inner side of the upper end. 
     The third cup  50   c  includes a third circumferential wall member  54   c  and a third liquid receiving member  55   c  and is placed adjacent to the second cup  50   b  at the opposite side to the first cup  50   a . The third circumferential wall member  54   c  stands up from the bottom portion  53  on an outer circumferential side of the second circumferential wall member  54   b  to be formed into a cylindrical shape. Also, a space between the third circumferential wall member  54   c  and the second circumferential wall member  54   b  serves as a third drain groove  503  for recovering and discharging the processing liquid and the like. 
     The third liquid receiving member  55   c  is formed so as to be continuous with an upper end of the third circumferential wall member  54   c . The third liquid receiving member  55   c  is formed to surround the periphery of the wafer W held by the rotation holder  31  and to extend to above the first liquid receiving member  55   a  and the second liquid receiving member  55   b.    
     As illustrated in  FIG. 9 , when both the first and second liquid receiving members  55   a  and  55   b  are at the respective retreat positions, an opening is formed at an inner side of an upper end of the third liquid receiving member  55   c  and a flow path leading from the opening to the third drain groove  503  is formed. 
     When the second liquid receiving member  55   b  is at the processing position, the third liquid receiving member  55   c  is in contact with the second liquid receiving member  55   b . Thus, the opening at the inner side of the upper end is closed, so that the flow path leading to the third drain groove  503  is blocked. 
     Drain ports  51   a  to  51   c  are formed in the bottom portions  53  of the first to third drain grooves  501  to  503 , respectively. 
     The drain port  51   a  is connected to a drain pipe  91   a . The drain pipe  91   a  is an example of a first drain line for discharging the processing liquid other than the organic processing liquid. Herein, the drain pipe  91   a  is used for discharging an acidic processing liquid. 
     A valve  62   a  is provided at a portion of the drain pipe  91   a . The drain pipe  91   a  is branched into a drain pipe  91   d  at a position of the valve  62   a . The drain pipe  91   a  is an example of a first drain line for discharging the processing liquid other than the organic processing liquid and is used herein for discharging the rinse liquid. For example, a three-way valve configured to be switched between a valve closing position, a position where a discharge path is opened toward the drain pipe  91   a  and a position where the drain path is opened toward the drain pipe  91   d  can be used as the valve  62   a.    
     The drain port  51   b  is connected to a drain pipe  91   b . The drain pipe  91   b  is an example of a first drain line for discharging the processing liquid other than the organic processing liquid and is used herein for discharging an alkaline processing liquid. Further, the drain port  51   c  is connected to a drain pipe  91   c . The drain pipe  91   c  is an example of a second drain line for discharging the organic processing liquid. 
     A valve  62   b  is provided at a portion of the drain pipe  91   b . Further, a valve  62   c  is provided at a portion of the drain pipe  91   c . The valves  62   a  to  62   c  are controlled by the control device  4 . 
     The substrate processing device  14 D performs a processing for switchably selecting any one of the drain ports  51   a  to  51   c  for the processing liquid by elevating the first liquid receiving member  55   a  of the first cup  50   a  or the second liquid receiving member  55   b  of the second cup  50   b  depending on the type of the processing liquid to be used. 
     For example, when processing the wafer W by discharging an etching liquid, which is the acidic processing liquid (hereinafter, referred to as “acidic processing liquid”), onto the wafer W, the control device  4  controls the driver  33  of the substrate holding mechanism  30  to open the valve  44   a  in a state where the rotation holder  31  is being rotated. 
     Here, the control device  4  keeps both the first cup  50   a  and the second cup  50   b  raised. That is, the control device  4  uses the first elevation mechanism  56  and the second elevation mechanism  57  to raise the first liquid receiving member  55   a  and the second liquid receiving member  55   b  to the respective processing positions. Thus, the flow path leading from the opening at the inner side of the upper end of the first liquid receiving member  55   a  to the first drain groove  501  is formed. As a result, the etching liquid supplied to the wafer W flows into the first drain groove  501 . 
     Also, the control device  4  controls the valve  62   a  to keep the discharge path open toward the drain pipe  91   a . Thus, the etching liquid which has flowed into the first drain groove  501  is drained to the outside of the substrate processing device  14 D through the drain pipe  91   a.    
     When processing the wafer W by discharging the rinse liquid onto the wafer W, the control device  4  controls the driver  33  of the substrate holding mechanism  30  to open the valve  44   b  in a state where the rotation holder  31  is being rotated. 
     Here, the control device  4  keeps both the first cup  50   a  and the second cup  50   b  raised. Further, the control device  4  controls the valve  62   a  to keep the discharge path open toward the drain pipe  91   d . Thus, the rinse liquid which has flowed into the first drain groove  501  is drained to the outside of the substrate processing device  14 D through the drain pipe  91   a  and the drain pipe  91   d.    
     In addition, when processing the wafer W by discharging the organic solvent, which is the organic processing liquid (hereinafter, referred to as “organic processing liquid”), onto the wafer W, the control device  4  controls the driver  33  of the substrate holding mechanism  30  to open the valve  44   c  in a state where the rotation holder  31  is being rotated. 
     Here, the control device  4  keeps both the first cup  50   a  and the second cup  50   b  lowered. That is, the control device  4  controls the first elevation mechanism  56  and the second elevation mechanism  57  to lower the first liquid receiving member  55   a  and the second liquid receiving member  55   b  to the respective retreat positions. Thus, the flow path leading from the opening at the inner side of the upper end of the third liquid receiving member  55   c  to the third drain groove  503  is formed. As a result, the organic solvent supplied to the wafer W flows into the third drain groove  503 . 
     Further, the control device  4  keeps the valve  62   c  open. Thus, the organic solvent which has flowed into the third drain groove  503  is drained to the outside of the substrate processing device  14 D through the drain pipe  91   c.    
     In addition, a source of the alkaline processing liquid (hereinafter, referred to as “alkaline processing liquid”) may be connected to the liquid supply  40 D. When processing the wafer W by discharging the alkaline processing liquid onto the wafer W, the control device  4  keeps only the second cup  50   b  between the first cup  50   a  and the second cup  50   b  raised. That is, the control device  4  controls the second elevation mechanism  57  to raise the second liquid receiving member  55   b  to the processing position. Thus, the flow path leading from the opening at the inner side of the upper end of the second liquid receiving member  55   b  to the second drain groove  502  is formed. As a result, the alkaline processing liquid supplied to the wafer W flows into the second drain groove  502 . Also, the control device  4  keeps the valve  62   b  open. Thus, the alkaline processing liquid which has flowed into the second drain groove  502  is drained to the outside of the substrate processing device  14 D through the drain pipe  91   b.    
     Exhaust ports  52   a ,  52   b  and  52   c  are formed in the bottom portion  53 , the first circumferential wall member  54   a  and the second circumferential wall member  54   b , respectively, of the recovery cup  50 . The exhaust ports  52   a ,  52   b , and  52   c  are connected to a single exhaust pipe, and the exhaust pipe is branched into first to third exhaust pipes  93   a  to  93   c  at the downstream side of the exhaust path. A valve  64   a  is provided at the first exhaust pipe  93   a , a valve  64   b  is provided at the second exhaust pipe  93   b , and a valve  64   c  is provided at the third exhaust pipe  93   c.    
     The first exhaust pipe  93   a  is an exhaust pipe for an acidic exhaust, the second exhaust pipe  93   b  is an exhaust pipe for an alkaline exhaust, and the third exhaust pipe  93   c  is an exhaust pipe for an organic exhaust. These exhaust pipes are switched by the control device  4  depending on the processings of the substrate processing. 
     For example, when performing a processing of generating the acidic exhaust, the control device  4  performs a switchover to the first exhaust pipe  93   a , and, thus, the acidic exhaust is exhausted through the valve  64   a . Likewise, when performing a processing of generating the alkaline exhaust, the control device  4  performs a switchover to the second exhaust pipe  93   b , and, thus, the alkaline exhaust is exhausted through the valve  64   b . Further, when performing a processing of generating the organic exhaust, the control device  4  performs a switchover to the third exhaust pipe  93   c , and, thus, the organic exhaust is exhausted through the valve  64   c.    
     The substrate processing device  14 D configured as described above further includes a separation unit configured to separate the organic solvent from the etching liquid supplied to the wafer W (hereinafter, referred to as “used etching liquid”) by the liquid supply  40 D. 
     The configuration of the separation unit will be described with reference to  FIG. 10 .  FIG. 10  is a diagram illustrating the configuration of the separation unit according to the fourth modification example. 
     As illustrated in  FIG. 10 , a separation unit  100  includes a heater  151 , a connection pipe  152 , and a cooler  153 . 
     The heater  151  is provided at the drain pipe  91   a  and configured to heat the used etching liquid flowing through the drain pipe  91   a . For example, an electric pipe heater used by being wound around the outer circumference of the drain pipe  91   a  may be used as the heater  151 . Since the heater  151  is provided at the drain pipe  91   a  so as to heat the used etching liquid flowing through the drain pipe  91   a , a size increase of the separation unit  100  can be suppressed. Therefore, it is possible to provide the separation unit  100  in a relatively narrow space. 
     The heater  151  is controlled by the control device  4  to heat the used etching liquid flowing through the drain pipe  91   a  to a temperature lower than the boiling point of water and higher than the boiling point of the organic solvent. As a result, if a liquid containing water flows into the drain pipe  91   a , it is possible to suppress vaporization of water along with the organic solvent by being heated with the heater  151  and to suppress introduction of the water into the drain pipe  91   c  through the connection pipe  152  to be described later. The organic solvent may be recovered by the manufacturer and then reused as, for example, boiler fuel. For this reason, by suppressing the introduction of the water into the drain pipe  91   c , it is possible to suppress the decrease of the utility value of the organic solvent caused by the introduction of the water when the organic solvent is reused. 
     The connection pipe  152  is an example of a connection line, and configured to connect the drain pipe  91   a  and the drain pipe  91   c  and guide the organic solvent, which has been vaporized by being heated with the heater  151 , to the drain pipe  91   c.    
     The cooler  153  is provided at the connection pipe  152 , and is configured to liquefy the organic solvent, which has been vaporized by being heated with the heater  151 , in the connection pipe  152 . The cooler  153  is, for example, a cooling jacket provided on the outer circumference of the drain pipe  91   c  and is configured to cool the vaporized organic solvent flowing through the drain pipe  91   c  with a coolant circulating therein. 
     The cooler  153  as the cooling jacket is not necessarily provided. In this case, the connection pipe  152  may be adjusted to a length sufficient to liquefy the vaporized organic solvent therein by natural heat dissipation. In this case, at least a part of the connection pipe  152  also functions as the cooler. 
     Then, specific operations of the substrate processing device  14 D will be described with reference to  FIG. 11 .  FIG. 11  is a flowchart illustrating a sequence of processings performed by the substrate processing system according to the fourth modification example. 
     As illustrated in  FIG. 11 , in the substrate processing device  14 D, a substrate carry-in processing is performed first (process S 201 ). Thus, the wafer W is held by the rotation holder  31  and rotates together with the rotation holder  31 . 
     Then, the substrate processing device  14 D performs an etching processing (process S 202 ). In the etching processing, the nozzle  41   a  of the liquid supply  40 D is located above the center of the wafer W. Thereafter, the valve  44   a  is opened for a predetermined time period and the etching liquid is supplied to the pattern forming surface of the wafer W. 
     In the etching processing, the first liquid receiving member  55   a  and the second liquid receiving member  55   b  are at the respective processing positions and the flow path leading from the opening at the inner side of the upper end of the first liquid receiving member  55   a  to the first drain groove  501  is formed. As a result, the used etching liquid supplied to the wafer W flows into the first drain groove  501  to be drained to the outside of the substrate processing device  14 D through the drain pipe  91   a.    
     The used etching liquid flowing through the drain pipe  91   a  is heated by the heater  151  provided at the drain pipe  91   a . Thus, the organic solvent contained in the used etching liquid is vaporized. The vaporized organic solvent flows through the connection pipe  152  to be liquefied by the cooler  153  provided at the connection pipe  152 , and is drained from the drain pipe  91   c  to the outside of the substrate processing device  14 D. 
     The organic processing liquid drained from the drain pipe  91   c  is recovered by, for example, the manufacturer and then reused as boiler fuel or the like. In the substrate processing device  14 D according to the fourth modification example, the organic solvent is separated from the used etching liquid to be discharged to the drain pipe  91   c . Therefore, it is possible to suppress the introduction of fluorine into the organic processing liquid discharged from the drain pipe  91   c . Thus, for example, when the recovered organic processing liquid is reused, it is not necessary to perform a process of removing the fluorine atoms from the recovered organic processing liquid. 
     For example, as a method for removing fluorine atoms from a waste liquid containing the fluorine atoms, a method in which calcium compounds such as slaked lime and calcium chloride are added to the waste liquid to be precipitated as calcium fluoride is known. In the substrate processing device  14 D according to the fourth modification example, such a process can be omitted. 
     Further, if a solvent for fluorine atoms is an organic solvent as in the etching liquid according to the exemplary embodiment, the removal efficiency of fluorine atoms with slaked lime or the like is lower than a case where a solvent for fluorine atoms is water. This is because the dielectric constant of the organic solvent is lower than that of water and slaked lime is difficult to dissolve in the organic solvent. 
     In this regard, in the substrate processing device  14 D according to the fourth modification example, the etching liquid containing fluorine atoms is discharged through the drain pipe  91   a  for discharging a processing liquid other than the organic processing liquid. For this reason, it is possible to suppress the introduction of fluorine atom into the drain pipe  91   c  for discharging the organic processing liquid. Further, the organic solvent is separated from the used etching liquid discharged to the drain pipe  91   a , and the separated organic solvent is discharged to the drain pipe  91   c  through the connection pipe  152 . Thus, the organic solvent contained in the used etching liquid can be recovered as an organic liquid effluent and reused as necessary. 
     In addition, in the method of removing fluorine atoms with slaked lime or the like, it takes several hours for the fluorine atoms and slaked lime to react. On the other hand, in the substrate processing device  14 D according to the fourth modification example, the organic solvent is separated from the used etching liquid by vaporizing the organic solvent contained in the used etching liquid, which does not need the time required for the reaction. Therefore, the organic solvent can be separated from the etching liquid in a short time compared with the method of removing fluorine atoms with slaked lime or the like. 
     Then, the substrate processing device  14 D performs a line cleaning processing (process S 203 ). The line cleaning processing is a processing of dissolving and discharging a salt remaining in the drain pipe  91   a  by allowing a cleaning liquid, which dissolves the salt containing fluorine atoms, to flow into the drain pipe  91   a.    
     In the line cleaning processing, the nozzle  41   c  of the liquid supply  40 D is located above the center of the wafer W. Thereafter, the valve  44   c  is opened for a predetermined time period and the organic solvent is supplied to the drain pipe  91   a  through the first drain groove  501 . The organic solvent supplied to the drain pipe  91   a  dissolves the salt remaining in the drain pipe  91   a , and the dissolved salt is drained together with the organic solvent from the drain pipe  91   a  to the outside of the substrate processing device  14 D. The control device  4  may stop the heating by the heater  151  during the line cleaning processing. Thus, it is possible to suppress the vaporization of the organic solvent serving as the cleaning liquid. 
     Subsequently, the substrate processing device  14 D performs a rinse processing (process S 204 ). In the rinse processing, the nozzle  41   b  of the liquid supply  40 D is located above the center of the wafer W. Thereafter, the valve  44   b  is opened for a predetermined time period and DIW, which is the rinse liquid, is supplied to the wafer W. The DIW supplied to the wafer W spreads on the pattern forming surface of the wafer W due to the centrifugal force caused by the rotation of the wafer W. As a result, the etching liquid or the organic solvent remaining on the wafer W is washed away by the DIW. 
     In the rinse processing, the discharge path is switched to the drain pipe  91   d  by the valve  62   a . Thus, the DIW supplied to the wafer W is drained to the outside of the substrate processing device  14 D through the drain pipe  91   d.    
     Then, the substrate processing device  14 D performs a dry processing (process S 205 ). In the dry processing, the nozzle  41   c  of the liquid supply  40 D is located above the center of the wafer W. Thereafter, the valve  44   c  is opened for a predetermined time period and the organic solvent is supplied to the wafer W. The organic solvent supplied to the wafer W spreads on the pattern forming surface of the wafer W due to the centrifugal force caused by the rotation of the wafer W. As a result, the DIW remaining on the wafer W is replaced with the organic solvent. Thereafter, the organic solvent on the wafer W is volatilized to dry the wafer W. 
     In the dry processing, the first liquid receiving member  55   a  and the second liquid receiving member  55   b  are at the respective retreat positions and the flow path leading from the opening at the inner side of the upper end of the third liquid receiving member  55   c  to the third drain groove  503  is formed. As a result, the organic solvent supplied to the wafer W flows into the third drain groove  503  to be drained to the outside of the substrate processing device  14 D through the drain pipe  91   c.    
     Subsequently, the substrate processing device  14 D performs a substrate carry-out processing (process S 206 ). In the substrate carry-out processing, the wafer W is taken out from the chamber  20  of the substrate processing device  14 D by the substrate transfer device  131  (see  FIG. 1 ). Thereafter, the wafer W is accommodated in the carrier C placed on the carrier placing section  11  via the delivery unit  122  and the substrate transfer device  121 . When the substrate carry-out processing is completed, the processing for one wafer W is completed. 
     As described above, in the substrate processing device  14 D according to the fourth modification example, the separation unit  100  can suppress the introduction of fluorine atoms into the organic liquid effluent. 
     (Fifth Modification Example) 
       FIG. 12  is a diagram illustrating a configuration of a separation unit according to a fifth modification example. A separation unit  100 E according to the fifth modification example illustrated in  FIG. 12  is configured to temporarily store the used etching liquid that flows through the drain pipe  91   a , and heat the used etching liquid being stored therein to vaporize the organic solvent contained in the used etching liquid. 
     Specifically, as illustrated in  FIG. 12 , the separation unit  100 E includes a reservoir  161 , a heater  162 , a liquid surface sensor  163 , a connection pipe  164  and a cooler  165 . 
     The reservoir  161  is a tank provided at a portion of the drain pipe  91   a  and stores the used etching liquid discharged to the drain pipe  91   a . The heater  162  is provided in the reservoir  161  and is configured to heat the used etching liquid stored in the reservoir  161 . The liquid surface sensor  163  is configured to detect a liquid surface of the liquid stored in the reservoir  161  and output the detection result to the control device  4 . 
     The connection pipe  164  is an example of a connection line that connects the reservoir  161  and the drain pipe  91   c  and discharges the organic solvent vaporized by the heating with the heater  162  to the drain pipe  91   c . The cooler  165  is provided at the connection pipe  164  and is configured to cool and liquefy the vaporized organic solvent flowing through the connection pipe  164 . 
     A valve  166  is provided on the drain pipe  91   a  at the downstream side of the reservoir  161 . Further, a coolant supply  167  is provided on the drain pipe  91   a  at the downstream side of the valve  166 . The coolant supply  167  includes a supply pipe  167   a  having one end connected to the drain pipe  91   a , a coolant source  167   b  connected to the other end of the supply pipe  167   a  and a valve  167   c  provided at a portion of the supply pipe  167   a.    
     In the etching processing, the used etching liquid discharged to the drain pipe  91   a  is stored in the reservoir  161  and heated by the heater  162  in the reservoir  161 . As a result, the organic solvent contained in the used etching liquid is vaporized, and the vaporized organic solvent is discharged to the drain pipe  91   c  through the connection pipe  164  and the cooler  165 . 
     Since the salt containing fluorine atoms remains in the reservoir  161 , a line cleaning processing is performed to remove the salt. In the line cleaning processing, the cleaning liquid (for example, water) supplied to the drain pipe  91   a  is stored in the reservoir  161  and thus dissolves the salt remaining in the reservoir  161 . 
     Thereafter, when the liquid surface is detected by the liquid surface sensor  163 , the control device  4  opens the valve  166  to discharge the liquid (mainly, cleaning liquid) stored in the reservoir  161 . Here, the liquid stored in the reservoir  161  has been heated by the heater  162 . Therefore, if the liquid is allowed to flow as it is, there is a possibility that vinyl chloride or the like used for a welded portion of the drain pipe  91   a  will be melted. For this reason, the control device  4  opens the valve  167   c  of the coolant supply  167  to supply the coolant (for example, water) from the coolant source  167   b  to the drain pipe  91   a . Thus, it is possible to protect the drain pipe  91   a.    
     As described above, the separation unit  100 E according to the fifth modification example stores the used etching liquid in the reservoir  161  and heats the used etching liquid in the reservoir  161  to separate the organic solvent. Thus, it is possible to suppress the organic solvent from being flown into the drain pipe  91   a , which is configured to discharge the processing liquid other than the organic solvent. 
     The separation unit  100 E may be provided for each substrate processing device  14 D, or may be provided for a plurality of substrate processing devices  14 D. 
     In the fourth modification example and the fifth modification example, the used etching liquid is discharged to the drain pipe  91   a . However, the used etching liquid is not necessarily discharged to the drain pipe  91   a . For example, a dedicated drain pipe for discharging the used etching liquid may be provided, and the used etching liquid may be discharged to the dedicated drain pipe. 
     In the fourth modification example, the organic solvent, which is used as the cleaning liquid in the line cleaning processing, is also used in the dry processing. However, the cleaning liquid used in the line cleaning processing is not necessarily identical to the organic solvent used in the dry processing. For example, an organic solvent (for example, ethanol) contained in the etching liquid may be used as the cleaning liquid, and an organic solvent (for example, IPA) other than ethanol may be used in the dry processing. 
     In the fourth modification example and the fifth modification example, the organic solvent is separated from the etching liquid according to the exemplary embodiment. However, a target processing liquid is not limited to the etching liquid according to the exemplary embodiment, but just needs to contain the fluorine atoms and the organic solvent. 
     The exemplary embodiments disclosed herein are illustrative and do not limit the present disclosure. In fact, the above exemplary embodiments can be embodied in various forms. Further, the above-described exemplary embodiments may be omitted, substituted, or changed in various forms without departing from the scope and spirit of the appended claims. 
     According to the present disclosure, it is possible to improve the selectivity of wet etching. 
     The claims of the present application are different and possibly, at least in some aspects, broader in scope than the claims pursued in the parent application. To the extent any prior amendments or characterizations of the scope of any claim or cited document made during prosecution of the parent could be construed as a disclaimer of any subject matter supported by the present disclosure, Applicants hereby rescind and retract such disclaimer. Accordingly, the references previously presented in the parent applications may need to be revisited.