JP2008244381A - Device and method for treating substrate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a substrate-treating device and substrate treatment method that minimizes the amount of chemical liquid consumption, and etches and removes an undesired substance satisfactorily from the surface periphery and rear of the substrate. <P>SOLUTION: The substrate W is supported nearly in a horizontal posture while the substrate W is separated upward from a spin base 15 by a prescribed distance. While a facing member 5 is arranged at a facing position at an upper portion on the substrate W, nitrogen gas is supplied to a space SP between a substrate surface Wf and a lower surface 501 of the facing member 5 from a plurality of gas discharge ports 502 and a gas supply route 57, and the substrate W is pressed against support pins F1-F6, S1-S6. A first nozzle 3 is positioned at a supply position P31 for supplying hydrochloric acid to the surface periphery TR on the rotating substrate W from the first nozzle 3, and a second nozzle 4 is positioned at a supply position P41 for supplying nitric acid to the surface periphery TR on the substrate W from the second nozzle 4, thus allowing the hydrochloric acid to react with the nitric acid on the substrate surface Wf to generate an etching liquid. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a semiconductor wafer, a glass substrate for photomask, a glass substrate for liquid crystal display, a glass substrate for plasma display, a substrate for FED (Field Emission Display), a substrate for optical disk, a substrate for magnetic disk, a substrate for magneto-optical disk, etc. The present invention relates to a substrate processing apparatus and method for performing a predetermined process on a substrate by supplying a processing liquid such as a chemical liquid or a rinsing liquid to the substrate.

  In a manufacturing process in which a series of processes are performed on a substrate such as a semiconductor wafer, a film forming process is performed to form various thin films on the surface of the substrate. In this film forming process, a film may be formed on the back surface of the substrate or the peripheral portion of the substrate surface. However, in general, only the circuit formation region at the center of the substrate surface needs to be formed on the substrate. If the film is formed on the back surface of the substrate or the peripheral portion of the substrate surface, the following problems occur. Sometimes. That is, in a subsequent process of the film forming process, the thin film formed on the peripheral portion of the substrate surface may be peeled off by contact with another apparatus. The peeled thin film may adhere to the circuit formation region at the center of the substrate surface or the substrate processing apparatus, which may cause a decrease in the yield of manufactured products and troubles in the substrate processing apparatus itself.

  Therefore, in order to remove the thin film formed on the back surface of the substrate or the peripheral portion of the substrate surface, a process of supplying a chemical solution to the back surface of the substrate or the peripheral portion of the substrate surface and etching away unnecessary thin films has been conventionally performed. ing.

  By the way, in recent manufacturing processes of semiconductor devices, platinum (Pt) is used as a film forming material. However, platinum (Pt) is hardly dissolved in a chemical solution that has been conventionally used as an etching solution, and aqua regia is used as an etching solution. (Mixture of hydrochloric acid and nitric acid) is used. Hereinafter, the etching removal process of platinum (Pt) by aqua regia will be described.

Aqua regia is produced by mixing a commercially available nitric acid stock solution (aqueous solution with a nitric acid concentration of 60%) and a commercially available hydrochloric acid stock solution (aqueous solution with a hydrochloric acid concentration of 35%) in a volume ratio of 1: 3. The reaction shown in is occurring.
HNO ₃ + 3HCl → NOCl + Cl ₂ + 2H ₂ O (Formula 1)
When nitrosyl chloride (NOCl) produced by the reaction of (Formula 1) reacts with Pt, Pt becomes chloroplatinate ion ([PtCl ₆ ] ²⁻ ) and dissolves, and Pt is removed by etching. .

  However, since aqua regia is very corrosive to metals, when aqua regia is prepared and held in the substrate processing apparatus, there is a possibility that parts constituting the substrate processing apparatus are corroded. Furthermore, aqua regia has a problem that the etching ability decreases with time after mixing hydrochloric acid and nitric acid. Therefore, in the apparatus described in Patent Document 1, in order to remove the metal film containing platinum formed on the back surface of the substrate and the peripheral portion of the substrate surface, the substrate is formed with the surface on which the circuit is formed facing downward. Is held on the stage, and nitric acid and hydrochloric acid are sequentially supplied from the back side of the upper substrate while the substrate is rotated. As a result, nitric acid and hydrochloric acid are supplied to the back and end surfaces of the substrate, and aqua regia is generated by mixing hydrochloric acid and nitric acid on the substrate. The aqua regia produces unnecessary metal near the back and end surfaces of the substrate. The film is etched away.

JP 2005-150571 A

  By the way, in the film formation process of the metal film with respect to the substrate, the metal film is formed on the surface of the substrate, and the metal slightly adheres to the back surface of the substrate. That is, the metal film formed on the peripheral portion of the front surface of the substrate is thicker than the metal film formed on the back surface of the substrate. However, in the apparatus described in Patent Document 1, hydrochloric acid and nitric acid are supplied from the back surface (surface on which the circuit of the substrate is not formed) side of the substrate, and these chemicals are supplied to the surface of the substrate (surface on which the circuit of the substrate is formed). Since the chemical solution is supplied to the surface peripheral portion of the substrate by wrapping around the peripheral portion, the aqua regia in which hydrochloric acid and nitric acid are sufficiently mixed is difficult to be supplied to the surface peripheral portion of the substrate. There is a problem that the time required for etching removal of the metal film formed on the portion becomes long.

  Moreover, in the apparatus described in Patent Document 1, the amounts of the chemicals supplied to the back surface and the peripheral edge of the front surface are equal. That is, almost the same amount of etching solution as that required to remove the unnecessary metal film adhering to the periphery of the front surface of the substrate is supplied to the back surface of the substrate. Since the attached metal film is thinner than the metal film attached to the peripheral edge of the front surface of the substrate, more chemical solution than necessary was supplied to the back surface of the substrate. In other words, there is a problem that the amount of the chemical solution is increased and the manufacturing cost is increased.

  The present invention has been made in view of the above problems, and provides a substrate processing apparatus and method that can satisfactorily etch unnecessary materials on the peripheral surface of the substrate surface and the back surface of the substrate while minimizing the consumption of the chemical solution. For the purpose.

  According to the first aspect of the present invention, there is provided a substrate holding means for holding the substrate with the surface of the substrate facing upward, a rotating means for rotating the substrate held by the substrate holding means, and a substrate held by the substrate holding means. First chemical liquid supply means for supplying the first chemical liquid toward the surface peripheral edge portion, and second chemical liquid supply means for supplying the second chemical liquid toward the surface peripheral edge portion of the substrate held by the substrate holding means, Corrosion is caused by mixing the first chemical liquid and the second chemical liquid supplied from the first chemical liquid supply means and the second chemical liquid supply means on the peripheral edge of the surface of the substrate held by the substrate holding means and rotated by the rotating means. The substrate processing apparatus is characterized in that a bevel etching solution having a property is generated and an unnecessary material on a peripheral portion of the surface of the substrate is etched by the bevel etching solution.

  According to this configuration, the substrate held by the substrate holding means is rotated by the rotating means, and the first chemical liquid and the second chemical liquid are directed from the first chemical liquid supply means and the second chemical liquid supply means toward the surface peripheral edge of the substrate. Is supplied. As a result, the first chemical liquid and the second chemical liquid are mixed on the peripheral edge of the surface of the substrate, and the first chemical liquid and the second chemical liquid react to generate a bevel etching liquid. And the unnecessary thing adhering to the surface peripheral part of a board | substrate is etched by this bevel etching liquid.

  Thus, even when the etching process is performed with a highly corrosive etching solution, the etching solution is generated on the surface of the substrate without being generated and held in advance in the substrate processing apparatus. It is possible to prevent corrosion of the parts of the device due to the liquid. Furthermore, since the first chemical solution and the second chemical solution are mixed on the peripheral edge portion of the surface of the substrate, etching is performed with an etching solution having a high etching capability immediately after mixing, so that the etching process is efficiently performed. In addition, the bevel etching liquid in the present invention is a liquid containing an etching component that is generated by a reaction between the first chemical liquid and the second chemical liquid and dissolves unnecessary substances. Furthermore, according to this configuration, the first chemical solution and the second chemical solution are sufficiently mixed on the surface peripheral portion of the substrate by supplying the first chemical solution and the second chemical solution directly toward the peripheral portion of the surface of the substrate. Therefore, the reaction between the first chemical liquid and the second chemical liquid is efficiently performed, and a bevel etching liquid that sufficiently contains an etching component is generated. As a result, unnecessary materials adhering to the peripheral edge of the surface of the substrate can be efficiently etched with the bevel etchant, and the time required for etching removal can be shortened.

  The invention according to claim 2 is a backside etching solution for supplying a backside etching solution generated by diluting and mixing the first chemical solution and the second chemical solution toward the back surface of the substrate held by the substrate holding means. The substrate processing apparatus according to claim 1, further comprising a supply unit.

  According to this configuration, the back surface etching solution generated by diluting and mixing the first chemical solution and the second chemical solution is supplied toward the back surface of the substrate, so that unnecessary substances attached to the back surface of the substrate are removed from the back surface. Etched with an etchant. Further, the back surface etching solution is prepared by diluting and mixing the first chemical solution and the second chemical solution in advance, so that the concentration of the etching component is substantially lower than that of the bevel etching solution. Since the unwanted material adhering to the back surface of the substrate is thinner than the unnecessary material adhering to the peripheral edge of the substrate surface, it is possible to supply a back surface etching solution having a substantially lower etching component concentration than the bevel etching solution. It is sufficiently etched away. Further, since the back surface etching solution has a low concentration of etching components, even if it is prepared in advance and held in the apparatus, the parts in the apparatus hardly corrode. As described above, the first chemical solution and the second chemical solution are directly supplied to the surface peripheral portion of the substrate, so that the etching process is performed by the bevel etchant generated on the surface peripheral portion of the substrate. The back surface of the substrate is preliminarily generated and is etched by a back surface etching solution having a concentration of etching components substantially lower than that of the bevel etching solution. It is possible to efficiently etch the unnecessary material. As described above, since the etching liquids having different etching component concentrations corresponding to the film thickness of the unwanted material are used, the chemical liquid is used efficiently, and the consumption of the chemical liquid can be suppressed.

  Further, the first chemical liquid supply means includes a first chemical liquid supply nozzle that supplies the first chemical liquid from the first supply position facing the surface peripheral edge of the substrate toward the surface peripheral edge of the substrate, the first supply position, and the substrate A first nozzle moving mechanism for moving the first chemical liquid supply nozzle between the first standby position separated from the upper side, and the second chemical liquid supply means is a position different from the first supply position, Between the 2nd chemical | medical solution supply nozzle which supplies a 2nd chemical | medical solution toward the surface peripheral part of a surface of a board | substrate from the 2nd supply position which opposes a surface peripheral part, and the 2nd standby position away from the 2nd supply position and the upper direction of a board | substrate And a second nozzle moving mechanism for moving the second chemical liquid supply nozzle, and the first chemical liquid supply nozzle and the second chemical liquid supply nozzle are positioned at the first and second supply positions, respectively. By discharging chemical solution from each nozzle, The undesired substances periphery may be etched.

  According to a fourth aspect of the present invention, the first nozzle moving mechanism and the second nozzle moving mechanism are configured by a common nozzle moving mechanism, and the first chemical liquid supply nozzle and the second chemical liquid supply nozzle move integrally. The substrate processing apparatus according to claim 3. As described above, since the nozzle moving mechanism is configured in common, the apparatus configuration can be simplified.

  According to a fifth aspect of the present invention, the first chemical solution supply nozzle and the second chemical solution supply nozzle are respectively arranged in close proximity to the surface of the substrate held by the substrate holding means and opposed to the peripheral edge of the surface of the substrate. The apparatus further includes a facing member having a plurality of nozzle insertion holes to be inserted, and the first and second nozzle moving mechanisms insert the first chemical liquid supply nozzle and the second chemical liquid supply nozzle into the plurality of nozzle insertion holes, respectively. 5. The substrate processing apparatus according to claim 3, wherein each nozzle is positioned at the first and second supply positions.

  According to this configuration, since the opposing member is disposed in close proximity to the substrate surface, the substrate surface can be reliably shielded from the external atmosphere around the substrate. Further, since the opposing member has a plurality of nozzle insertion holes into which the first chemical liquid supply nozzle and the second chemical liquid supply nozzle are respectively inserted at positions facing the peripheral edge of the surface of the substrate, each nozzle is used as a nozzle insertion hole. By inserting, it can be arranged to oppose the peripheral edge of the surface of the substrate. Therefore, the first chemical solution and the second chemical solution are directly applied to the peripheral edge of the surface of the substrate while preventing the first and second chemical solutions from adhering to the central portion (non-treatment region) of the substrate surface by the facing member that covers the substrate surface. The unnecessary material can be satisfactorily etched. In addition, since the first chemical liquid supply nozzle and the second chemical liquid supply nozzle are inserted into the nozzle insertion holes of the opposing member, the first and second chemical liquids are scattered during the etching process, and a large amount of the first and second chemical liquid nozzles are supplied to the nozzle. The chemical solution will not adhere. For this reason, when the nozzle is moved, the first and second chemical liquids are prevented from dropping from the nozzle and adhering to the substrate or the peripheral member of the substrate.

  In the invention according to claim 6, the facing member has a substrate facing surface facing the surface of the substrate held by the substrate holding means, and a gas discharge port is formed on the substrate facing surface. A rotating member provided rotatably around a vertical axis, and at least three or more supporting members projecting upward from the rotating member and contacting the back surface of the substrate and supporting the substrate apart from the rotating member; 6. The substrate processing according to claim 5, further comprising a gas supply unit that presses the substrate against the support member by supplying gas from a gas discharge port to a space sandwiched between the substrate facing surface and the surface of the substrate. Device.

  According to this configuration, the substrate is supported by being separated by at least three or more support members that are in contact with the back surface of the substrate, and is pressed against the support member by the gas supplied from the gas supply unit to the substrate surface. Retained. The rotating means rotates the rotating member, and the substrate pressed by the supporting member rotates with the rotating member while being supported by the supporting member by the frictional force generated between the supporting member and the substrate. Since the holding member that holds the substrate in contact with the outer peripheral edge of the substrate by holding the substrate on the rotating member in this manner can be made unnecessary, the first and second chemicals that are shaken off radially outward from the substrate. Does not hit the holding member and bounce back to the substrate surface. Accordingly, it is possible to satisfactorily etch unwanted materials from the peripheral edge of the surface of the substrate.

  Further, the first chemical solution may be hydrochloric acid, and the second chemical solution may be nitric acid. In this case, nitrosyl chloride is generated in the bevel etching solution or the back surface etching solution by causing the reaction shown in (Formula 1) between hydrochloric acid and nitric acid. Thereby, the etching process of the metal film containing platinum (Pt) can be performed.

  The invention according to claim 8 is a first chemical supply that is performed in parallel with the substrate holding and rotating step for holding and rotating the substrate and the substrate holding and rotating step, and supplies the first chemical toward the peripheral edge of the surface of the substrate. Performed in parallel with the step, the substrate holding rotation step and the first chemical solution supplying step, and supplied by the second chemical solution supplying step and the first chemical solution supplying step for supplying the second chemical solution toward the surface peripheral edge of the substrate. The bevel which etches the unnecessary thing of the surface peripheral part of a substrate with the bevel etching liquid generated when the 1st chemical liquid and the 2nd chemical liquid supplied by the 2nd chemical solution supply process are mixed on the surface peripheral part of a substrate And a substrate processing method comprising: an etching step.

  By this method, the same effect as that of the first aspect of the invention can be realized.

<First Embodiment>
FIG. 1 is a diagram showing a first embodiment of a substrate processing apparatus according to the present invention. FIG. 2 is a block diagram showing a main control configuration of the substrate processing apparatus of FIG. This substrate processing apparatus is an apparatus that etches and removes a thin film (unnecessary material) present on the peripheral portion of the surface Wf of the substrate W or a thin film present on the peripheral portion and the substrate back surface Wb. On the substrate W to be processed, a metal film made of platinum is formed on the substrate surface Wf or the front and back surfaces Wf, Wb. Therefore, when a thin film is formed only on the substrate surface Wf, a chemical solution and a rinsing solution such as pure water or DIW (hereinafter, chemical solution and rinsing solution are collectively referred to as a peripheral portion TR (treatment region) of the substrate surface Wf. The thin film is removed from the peripheral portion TR by etching, and the processing liquid is supplied to the substrate back surface Wb to clean the back surface Wb. When thin films are formed on the front and back surfaces Wf and Wb of the substrate W, the processing liquid is supplied to the front surface peripheral portion TR and the back surface Wb, and the thin film is etched away from the front surface peripheral portion TR and the back surface Wb. In this embodiment, the substrate surface Wf refers to a device formation surface on which a device pattern is formed (surface on which a substrate circuit is formed).

  The substrate processing apparatus includes a spin chuck 1 (corresponding to the “substrate holding means” of the present invention) that rotates the substrate W while maintaining the substrate surface Wf facing upward, and holds the substrate W on the spin chuck 1. The processing liquid is supplied from the substrate surface side to the front surface peripheral portion TR of the substrate W held by the spin chuck 1 from the lower surface processing nozzle 2 for supplying the processing liquid toward the center of the lower surface (back surface Wb) of the substrate W. A first nozzle 3 that performs processing, a second nozzle 4 that supplies a processing liquid to the surface peripheral portion TR of the substrate W held on the spin chuck 1 from the substrate surface side, and a surface Wf of the substrate W held on the spin chuck 1. And an opposing member 5 arranged to face each other.

  The spin chuck 1 has a hollow rotating support shaft 11 connected to a rotating shaft of a chuck rotating mechanism 13 (corresponding to the “rotating means” of the present invention) including a motor. It can be rotated. A spin base 15 is integrally connected to the upper end portion of the rotating spindle 11 by a fastening part such as a screw. Therefore, the spin base 15 rotates around the rotation center A0 by driving the chuck rotation mechanism 13 in accordance with an operation command from the control unit 8 that controls the entire apparatus. Thus, in this embodiment, the spin base 15 functions as the “rotating member” of the present invention.

  A processing liquid supply pipe 21 is inserted into the hollow rotating spindle 11, and the lower surface processing nozzle 2 is coupled to the upper end of the processing liquid supply pipe 21. The treatment liquid supply pipe 21 is connected to the chemical liquid supply unit 16 and the DIW supply unit 17, and DIW is selectively supplied as a back surface etching liquid or a rinsing liquid generated by mixing hydrochloric acid and nitric acid in advance as the chemical liquid. Thus, in this embodiment, the lower surface processing nozzle 2, the processing liquid supply pipe 21, and the chemical liquid supply unit 16 function as the “back surface etching liquid supply means” of the present invention. Further, a gap between the inner wall surface of the rotation spindle 11 and the outer wall surface of the processing liquid supply pipe 21 forms an annular gas supply path 23. The gas supply path 23 is connected to the gas supply unit 18 and can supply nitrogen gas into a space sandwiched between the substrate back surface Wb and the top surface of the spin base 15 facing the substrate back surface Wb. In this embodiment, nitrogen gas is supplied from the gas supply unit 18, but air or other inert gas may be discharged.

  FIG. 3 is a plan view of the spin base 15 as viewed from above. An opening is provided at the center of the spin base 15. Further, a plurality (six in this embodiment) of first support pins F1 to F6 and a plurality (six in this embodiment) of second support pins S1 to S6 are provided near the periphery of the spin base 15. The “supporting member” of the present invention is provided so as to be vertically movable. The first support pins F1 to F6 project radially upward from the spin base 15 at substantially equal angular intervals about the rotation center A0, and the second support pins S1 to S6 extend along the circumferential direction. Projecting upward from the spin base 15 at substantially equal angular intervals radially about the rotation center A0 so as to be positioned between the first support pins F1 to F6. That is, a pair of support pins including the first and second support pins are provided in a radial direction around the rotation center A0 and six pairs in a radial direction, and upward on the peripheral edge of the spin base 15.

  Each of the first support pins F1 to F6 and the second support pins S1 to S6 can support the substrate W in a substantially horizontal posture while being spaced apart from the spin base 15 by a predetermined distance by contacting the back surface Wb of the substrate. It has become. Among these, six first support pins F1 to F6 arranged alternately every other along the circumferential direction constitute a first support pin group, and these support the substrate W in conjunction with each other or the back surface of the substrate. It operates so as to release the support away from Wb. On the other hand, the remaining six second support pins S1 to S6 constitute a second support pin group that supports the substrate W in conjunction with each other or releases the support away from the substrate back surface Wb. Operate. In order to horizontally support the substrate W, each support pin group may have at least three support pins, but each support pin group should have six support pins. Thus, the substrate W can be stably supported.

  FIG. 4 is a partially enlarged view showing the structure of the support pin. Since each of the support pins F1 to F6 and S1 to S6 has the same configuration, only the configuration of one support pin F1 will be described here with reference to the drawings. The support pin F1 includes an abutting portion 61 that can be separated from and abutted on the lower surface of the substrate W, a movable rod 62 that supports the abutting portion 61 so as to be movable up and down, and a lift drive unit that includes a motor that moves the movable rod 62 up and down. 63 and a bellows 64 provided so as to surround the movable rod 62 and blocking the movable rod 62 and the lifting drive unit 63 from the external atmosphere. The bellows 64 is formed of PTFE (polytetrafluoroethylene), for example, and protects the movable rod 62 formed of stainless steel (SUS) or aluminum when the substrate W is processed with a chemical solution or the like. The contact portion 61 is preferably formed of PCTFE (polychlorotrifluoroethylene) in consideration of chemical resistance. The upper end portion of the bellows 64 is fixed to the lower surface side of the contact portion 61, while the lower end portion of the bellows 64 is fixed to the upper surface side of the spin base 15.

  In the support pins F1 to F6 and S1 to S6 having the above-described configuration, the elevating drive unit 63 moves the movable rod 62 with a stroke of 1 to several mm via a drive connecting unit (not shown) based on a drive signal from the control unit 8. By driving, the substrate W is supported as follows. That is, in a state where the elevating drive unit 63 is not driven, each of the support pins F1 to F6 and S1 to S6 is urged by a coil spring or the like so as to support the substrate W at a predetermined height position (substrate processing position). The substrate W is urged upward by a support pin group including both a first support pin group including support pins F1 to F6 and a second support pin group including support pins S1 to S6. Supported. On the other hand, when the support pins S1 to S6 are driven downward against the urging force, the contact portions 61 of the support pins S1 to S6 are separated from the substrate back surface Wb, and the substrate W is the first composed of the support pins F1 to F6. It is supported only by the support pin group. When the support pins F1 to F6 are driven downward against the urging force, the contact portions 61 of the support pins F1 to F6 are separated from the substrate back surface Wb, and the substrate W is the second support composed of the support pins S1 to S6. Supported only by pins.

  Returning to FIG. 1, the description will be continued. Above the spin chuck 1, a disk-like facing member 5 that faces the substrate W supported by the support pins F1 to F6 and S1 to S6 is horizontally disposed. The facing member 5 is attached to a lower end portion of a rotation support shaft 51 arranged coaxially with the rotation support shaft 11 of the spin chuck 1 so as to be integrally rotatable. A counter member rotation mechanism 53 is connected to the rotation support shaft 51, and the counter member 5 is driven around the rotation center A0 by driving the motor of the counter member rotation mechanism 53 in accordance with an operation command from the control unit 8. Rotate. The control unit 8 controls the counter member rotating mechanism 53 to synchronize with the chuck rotating mechanism 13, thereby rotating the counter member 5 with the same rotation direction and the same rotation speed as the spin chuck 1.

  Further, the facing member 5 is connected to the facing member lifting mechanism 55 and operates the lifting drive actuator (for example, an air cylinder) of the facing member lifting mechanism 55 so that the facing member 5 is opposed to the spin base 15 in the vicinity. Or can be separated. Specifically, the control unit 8 drives the counter member lifting mechanism 55 so that when the substrate W is loaded into or unloaded from the substrate processing apparatus, the control unit 8 faces a separated position sufficiently away from the spin chuck 1. The member 5 is raised. On the other hand, when a predetermined process such as an etching process is performed on the substrate W, the facing member 5 is lowered to a facing position set very close to the surface Wf of the substrate W held by the spin chuck 1. . As a result, the lower surface 501 (corresponding to the substrate facing surface of the present invention) of the facing member 5 and the substrate surface Wf are disposed to face each other.

  The central opening of the facing member 5 and the hollow portion of the rotation support shaft 51 form a gas supply path 57. The gas supply path 57 is connected to the gas supply unit 18 (corresponding to the “gas supply unit” of the present invention) and can supply nitrogen gas to the space SP sandwiched between the substrate surface Wf and the lower surface 501 of the opposing member 5. It has become.

  FIG. 5 is a bottom view of the facing member 5. The plane size of the lower surface 501 of the facing member 5 is formed to be equal to or larger than the diameter of the substrate W. For this reason, when the facing member 5 is disposed at the facing position, the entire surface of the substrate is covered and the atmosphere on the substrate surface Wf can be blocked from the external atmosphere. In addition, nozzle insertion holes 5A and 5B having a substantially cylindrical inner space penetrating the opposing member 5 in the vertical direction (vertical axis direction) are formed in the peripheral portion of the opposing member 5. The nozzles 3 and 4 can be inserted individually. The nozzle insertion hole 5A and the nozzle insertion hole 5B are formed in the same shape at symmetrical positions with respect to the rotation center A0. On the other hand, the first nozzle 3 and the second nozzle 4 have the same nozzle outer diameter. For this reason, both the nozzles 3 and 4 can be inserted into any of the nozzle insertion holes 5A and 5B.

  A plurality of gas discharge ports 502 are formed on the lower surface 501 of the facing member 5. The plurality of gas discharge ports 502 are circumferentially centered on the rotation center A0 at a position facing the central portion of the surface of the substrate W held by the spin chuck 1, that is, the non-process region NTR radially inward of the surface peripheral portion TR. Are formed at equiangular intervals. These gas discharge ports 502 communicate with a gas circulation space 503 (FIG. 1) formed inside the facing member 5, and when nitrogen gas is supplied to the gas circulation space 503, a plurality of gas discharge ports 502 are connected. Through this, nitrogen gas is supplied to the space SP.

  When nitrogen gas is supplied to the space SP from the plurality of gas discharge ports 502 and the gas supply path 57 in a state where the opposing member 5 is positioned at the opposing position, the internal pressure of the space SP is increased and the substrate W is The support pins F1 to F6 and S1 to S6 that are in contact with the back surface Wb are pressed. Accordingly, when the spin base 15 rotates according to the operation command of the control unit 8, the substrate W is supported by the support pins F1 to F6 by the frictional force generated between the substrate back surface Wb and the support pins F1 to F6 and S1 to S6. It rotates with the spin base 15 while being supported by S1 to S6. Note that the nitrogen gas supplied to the space SP flows outward in the radial direction of the substrate W.

  Returning to FIG. 1, the description will be continued. The first nozzle 3 is connected to the chemical solution supply unit 16 and the DIW supply unit 17, and DIW is supplied from the chemical solution supply unit 16 or the DIW supply unit 17 as a chemical solution or hydrochloric acid or a rinse solution in response to an operation command from the control unit 8. 1 nozzle 3 is selectively supplied. In this embodiment, in order to etch away the thin film made of platinum from the substrate W, a relatively high concentration of hydrochloric acid (for example, a commercially available hydrochloric acid stock solution that is an aqueous solution having a hydrochloric acid concentration of 35%) is prepared. Thus, the chemical liquid supply unit 16 and the first nozzle 3 correspond to the “first chemical liquid supply means” of the present invention, the first nozzle 3 corresponds to the “first chemical liquid supply nozzle”, and hydrochloric acid is the “first chemical liquid supply unit”. Is equivalent to.

  The first nozzle 3 is attached to one end of a nozzle arm 31 extending in the horizontal direction. The other end of the nozzle arm 31 is connected to the first nozzle moving mechanism 33. The first nozzle moving mechanism 33 can swing the first nozzle 3 in the horizontal direction around a predetermined rotation axis and raise and lower the first nozzle 3. For this reason, the first nozzle moving mechanism 33 is driven in accordance with an operation command from the control unit 8, whereby the first nozzle 3 is inserted into the nozzle insertion hole 5 </ b> A (or 5 </ b> B) of the facing member 5 and the surface periphery It can be moved to a supply position P31 (corresponding to the “first supply position” of the present invention) where hydrochloric acid or DIW can be supplied to TR and a standby position P32 away from the substrate W.

  The second nozzle 4 is also connected to the chemical solution supply unit 16 and the DIW supply unit 17, and in response to an operation command from the control unit 8, the chemical solution supply unit 16 or the DIW supply unit 17 outputs DIW as nitric acid or rinse solution as the chemical solution. Is selectively supplied to the second nozzle 4. In this embodiment, a relatively high concentration of nitric acid (for example, a commercially available nitric acid stock solution that is an aqueous solution having a nitric acid concentration of 60%) is prepared in order to etch away the thin film made of platinum from the substrate W. Thus, the chemical solution supply unit 16 and the second nozzle 4 correspond to the “second chemical solution supply means” of the present invention, the second nozzle 4 corresponds to the “second chemical solution supply nozzle”, and the nitric acid is “the second chemical solution”. Is equivalent to. The liquid used for the rinsing liquid may be carbonated water, hydrogen water, dilute concentration (for example, about 1 ppm) ammonia water, dilute hydrochloric acid, or the like in addition to DIW.

  The second nozzle moving mechanism 43 that drives the second nozzle 4 has the same configuration as the first nozzle moving mechanism 33. That is, the second nozzle moving mechanism 43 can swing the second nozzle 4 attached to the tip of the nozzle arm 41 in the horizontal direction around a predetermined rotation axis and raise and lower the second nozzle 4. For this reason, the second nozzle moving mechanism 43 is driven in accordance with an operation command from the control unit 8, whereby the second nozzle 4 is inserted into the nozzle insertion hole 5 </ b> B (or 5 </ b> A) of the facing member 5 and the surface peripheral edge portion It can be moved to a supply position P41 (corresponding to the “second supply position” of the present invention) where nitric acid or DIW can be supplied to TR and a standby position P42 away from the substrate W.

  Here, the nozzle insertion hole 5A and the nozzle insertion hole 5B are formed at symmetrical positions with respect to the rotation center A0, and extend in a plan view from the rotation center A0 to the supply position P31 and from the rotation center A0 to the supply position P41. The angle formed by the direction is 180 °.

  With the above configuration, the control unit 8 drives the first and second nozzle moving mechanisms 33 and 43 while controlling the chemical solution supply unit 16 and the DIW supply unit 17, so that the first nozzle 3 positioned at the supply position P31 While supplying hydrochloric acid to the surface peripheral portion TR of the rotating substrate W, the second nozzle 4 is positioned at the supply position P41 and nitric acid is supplied to the surface peripheral portion TR of the substrate W.

  Next, the configuration of the nozzle insertion holes 5A and 5B provided in the first and second nozzles 3 and 4 and the facing member 5 will be described. Both nozzles 3 and 4 are configured identically. Both nozzle insertion holes 5A and 5B have the same shape as the opposing member 5, and are formed symmetrically with respect to the rotation center A0. Therefore, only the configuration of the first nozzle 3 and the nozzle insertion hole 5A will be described with reference to FIG.

  FIG. 6 is a diagram illustrating the configuration of the nozzle insertion hole 5 </ b> A provided in the first nozzle 3 and the facing member 5. The first nozzle 3 is formed in a substantially cylindrical shape in accordance with the shape of the nozzle insertion hole 5A provided in the facing member 5, and is inserted into the nozzle insertion hole 5A so that the front end side of the first nozzle 3 is the surface peripheral portion TR. It arranges facing (FIG. 1). A liquid supply path 301 is formed inside the first nozzle 3, and the tip (lower end) of the liquid supply path 301 constitutes the discharge port 301 a of the first nozzle 3. The nozzle outer diameter of the first nozzle 3 is, for example, about φ5 to 6 mm so as not to increase the diameter of the nozzle insertion hole 5A more than necessary. The 1st nozzle 3 is comprised so that the cross-sectional area of the nozzle trunk | drum formed in the substantially cylindrical shape may differ on the nozzle front end side and a rear end side. Specifically, the cross-sectional area of the body 302 on the nozzle front end side is configured to be smaller than the cross-sectional area of the body 303 on the nozzle rear end side, and the body 302 on the nozzle front end side and the nozzle rear end side on the nozzle rear end side are configured. A step surface 304 is formed between the body portion 303 and the body portion 303. That is, the outer peripheral surface (side surface) of the body 302 on the nozzle front end side and the outer peripheral surface (side surface) of the body 303 on the rear end side of the nozzle are connected via the step surface 304. The step surface 304 is formed so as to surround the body portion 302 on the nozzle tip side and substantially parallel to the substrate surface Wf held by the spin chuck 1.

  An annular contact surface 504 that can contact the step surface 304 of the first nozzle 3 is formed on the inner wall of the nozzle insertion hole 5A. When the first nozzle 3 is inserted into the nozzle insertion hole 5A, the step surface 304 and the contact surface 504 come into contact with each other, whereby the first nozzle 3 is positioned at the supply position P31. In a state where the first nozzle 3 is positioned at the supply position P <b> 31, the front end surface around the discharge port 301 a of the first nozzle 3 is flush with the facing surface 501 of the facing member 5. The contact surface 504 is formed substantially parallel to the facing surface 501 of the facing member 5, that is, substantially parallel to the substrate surface Wf, and is in surface contact with the step surface 304 of the first nozzle 3. For this reason, when positioning the 1st nozzle 3 in supply position P31, the 1st nozzle 3 contact | abuts to the opposing member 5, the position is fixed, and the 1st nozzle 3 can be positioned stably.

  The discharge port 301a of the first nozzle 3 opens toward the outside in the radial direction of the substrate W, and hydrochloric acid or DIW can be discharged from the discharge port 301a to the surface peripheral portion TR. The liquid supply path 301 is connected to the chemical supply unit 16 and the DIW supply unit 17 at the rear end of the nozzle, and can selectively discharge hydrochloric acid or DIW. For this reason, when hydrochloric acid is pumped from the chemical solution supply unit 16 to the liquid supply path 301, the hydrochloric acid is discharged from the first nozzle 3 toward the radially outer side of the substrate W. As a result, the hydrochloric acid supplied to the surface peripheral portion TR flows toward the outside in the radial direction of the substrate W and is discharged out of the substrate. Accordingly, hydrochloric acid is not supplied to the non-process region NTR radially inward of the hydrochloric acid supply position, and hydrochloric acid is supplied to the thin film portion having a certain width (surface peripheral portion TR) from the end surface of the substrate W inward. (FIG. 8A). When DIW is pumped from the DIW supply unit 17 to the liquid supply path 301, DIW is discharged from the first nozzle 3 toward the outside in the radial direction of the substrate W. As a result, chemical components such as hydrochloric acid adhering to the surface peripheral portion TR are washed away with DIW. Similarly to the first nozzle 3, the discharge port of the second nozzle 4 is opened outward in the radial direction of the substrate W, and nitric acid or DIW can be discharged from the discharge port to the surface peripheral portion TR. (FIG. 8B).

  FIG. 7 is a diagram schematically showing the chemical solution supply unit 16.

  The chemical solution supply unit 16 includes a hydrochloric acid tank 161 for storing hydrochloric acid (a commercially available hydrochloric acid stock solution having a hydrochloric acid concentration of 35%) and a nitric acid tank 162 for storing nitric acid (a commercially available nitric acid stock solution having a 60% nitric acid concentration). , And a liquid mixture tank 163 for storing a liquid mixture produced by mixing hydrochloric acid and nitric acid. A pipe 164 is connected to the hydrochloric acid tank 161, and a pipe 165 is branched and connected to the pipe 164. By feeding nitrogen gas into the hydrochloric acid tank 161, hydrochloric acid is supplied to the first nozzle 3 or the liquid mixture tank 163. It can be supplied. That is, valves 166 and 167 are interposed in the pipes 164 and 165, respectively, and the valve 167 is closed. By opening the valve 166, hydrochloric acid is supplied to the first nozzle 3, while the valve 166 is closed. When the valve 167 is opened, hydrochloric acid is supplied to the mixed solution tank 163. Similarly to the hydrochloric acid tank 161, the nitric acid tank 162 is connected to a pipe 168. A pipe 169 is branched and connected to the pipe 168, and nitrogen gas is pumped into the nitric acid tank 162, so that the second nozzle 4 or the mixed liquid is used. Nitric acid can be supplied to the tank 163. That is, valves 170 and 171 are interposed in the pipes 168 and 169, respectively, and when the valve 171 is closed and the valve 170 is opened, nitric acid is supplied to the second nozzle 4, while the valve 170 is When the valve 171 is opened while being closed, nitric acid is supplied to the liquid mixture tank 163. The mixed solution tank 163 is supplied with hydrochloric acid, nitric acid, and DIW, and the respective solutions are mixed to generate and store a back surface etching solution. In this embodiment, hydrochloric acid and nitric acid are supplied so that the mixing ratio of hydrochloric acid and nitric acid is hydrochloric acid: nitric acid = 3: 1 by volume. Furthermore, by supplying DIW, the mixed solution (aqua regia) of hydrochloric acid and nitric acid is stored in the mixed solution tank 163 in a state of being diluted twofold. A mixture of hydrochloric acid and nitric acid (aqua regia) is very corrosive to metals and may corrode parts that make up the substrate processing equipment. As in this embodiment, aqua regia is diluted with DIW. By holding in such a state, the apparatus can be prevented from corroding.

  A pipe 172 is connected to the mixed liquid tank 163, and a pump interposed in the pipe 172 is driven to supply the back surface etching liquid to the bottom surface processing nozzle 2.

  FIG. 8 is a cross-sectional view when the first and second nozzles 3 and 4 are inserted into the nozzle insertion holes 5A and 5B, respectively. The hole diameters of the nozzle insertion holes 5A and 5B are formed larger than the outer diameters of the first and second nozzles 3 and 4. For this reason, the first and second nozzles 3 and 4 can be positioned at different positions in the horizontal direction in the internal space of the nozzle insertion holes 5A and 5B. The diameters of the nozzle insertion holes 5A and 5B are preferably larger than the outer diameters of the first and second nozzles 3 and 4 by about 1 to 2 mm. In this case, the supply position P31 and the supply position P41 can be set so that the radial distance from the peripheral end surface of the substrate W is different by about 0.2 to 0.5 mm. In this embodiment, the supply position P31 of the first nozzle 3 and the supply position P41 of the second nozzle 4 are set such that the radial distance from the peripheral end surface of the substrate W is the same.

  A gas introduction port 505 is opened on the inner walls of the nozzle insertion holes 5A and 5B of the opposing member 5, and nitrogen gas can be supplied from the gas introduction port 505 to the internal spaces of the nozzle insertion holes 5A and 5B. Yes. The gas inlet 505 communicates with the gas supply unit 18 through a gas circulation space 503 formed inside the facing member 5. Therefore, when nitrogen gas is pumped from the gas supply unit 18, the nitrogen gas is supplied to the internal spaces of the nozzle insertion holes 5A and 5B. Thus, in a state where the first and second nozzles 3 and 4 are positioned at the standby positions P32 and P42, that is, in a state where the first and second nozzles 3 and 4 are not inserted into the nozzle insertion holes 5A and 5B, the nozzles Nitrogen gas is ejected from both the upper and lower openings of the insertion holes 5A and 5B. For this reason, even when the nozzle is not inserted into the nozzle insertion holes 5A and 5B, the treatment liquid is prevented from adhering to the inner walls of the nozzle insertion holes 5A and 5B.

  Next, the operation of the substrate processing apparatus configured as described above will be described with reference to FIGS. FIG. 9 is a flowchart showing the operation of the substrate processing apparatus of FIG. FIG. 10 is a plan view for explaining the action of removing the thin film by the chemical solution.

  In this apparatus, when an unprocessed substrate W is carried into the apparatus, the control unit 8 controls each part of the apparatus to perform a series of film removal processes on the substrate W (chemical treatment process + rinsing process + drying process). Is executed. Here, a thin film TF (FIG. 8) made of a metal film containing platinum is formed on the substrate surface Wf. That is, the substrate surface Wf is a thin film forming surface. Therefore, in this embodiment, the substrate W is carried into the apparatus with the substrate surface Wf facing upward. Note that the facing member 5 is in a separated position, and prevents interference with the substrate W.

  When the unprocessed substrate W is placed on the support pins F1 to F6 and S1 to S6, nitrogen gas is discharged from the gas discharge port 502 of the facing member 5 at the separated position, and nitrogen gas is discharged from the gas supply path 57. Discharge (step 1). Next, the opposing member 5 is rotated, and the opposing member 5 is positioned with respect to the rotation direction so that the nozzle insertion holes 5A and 5B are at predetermined positions (step 2). Thereafter, the facing member 5 is lowered to the facing position and is disposed close to the substrate surface Wf (step S3). As a result, the internal pressure of the space SP sandwiched between the lower surface 501 of the opposing member 5 and the substrate surface Wf is increased, and the substrate W is pressed against the support pins F1 to F6 and S1 to S6 that are in contact with the lower surface (back surface Wb). And held on the spin base 15. Further, the substrate surface Wf is covered with the lower surface 501 of the facing member 5 and is reliably shielded from the external atmosphere around the substrate. As described above, the substrate W may be supported by all the support pins F1 to F6 and S1 to S6, or may be supported only by the first support pin group including the support pins F1 to F6, or may be supported. You may support only by the 2nd support pin group which consists of pins S1-S6.

  Next, the substrate W is rotated while the facing member 5 is stopped (step S4; corresponding to the substrate holding and rotating step of the present invention). At this time, the substrate W pressed by the support pins F1 to F6 and S1 to S6 is held by the spin base 15 by the frictional force generated between the support pins F1 to F6 and S1 to S6 and the substrate back surface Wb. 15 and rotate. Subsequently, the first nozzle 3 is positioned from the standby position P32 to the supply position P31 (step S5). Specifically, the first nozzle 3 is moved to a position above the nozzle insertion hole 5A of the facing member 5 along the horizontal direction. Then, the first nozzle 3 is lowered and inserted into the nozzle insertion hole 5A. At the same time when the first nozzle 3 is positioned at the supply position P31, the second nozzle 4 is also positioned from the standby position P42 to the supply position P41 (step S5).

  When the rotation speed of the substrate W reaches a predetermined speed (for example, 600 rpm), the chemical solution supply unit 16 is operated, and the chemical solution is simultaneously discharged from the first nozzle 3 and the second nozzle 4 to the surface peripheral portion TR of the rotating substrate W. In each case, hydrochloric acid and nitric acid are continuously supplied. As a result, the thin film is etched away from the surface peripheral portion TR and the substrate end surface portion connected to the surface peripheral portion TR over the entire circumference (step S6).

  Specifically, platinum is insoluble in both hydrochloric acid and nitric acid when only hydrochloric acid is attached to the surface peripheral portion TR on which the metal film containing platinum is formed or only nitric acid is attached. Therefore, the thin film TF on the surface peripheral portion TR is not removed by etching. However, as shown in FIG. 10, after hydrochloric acid is supplied from the first nozzle 3 to the micro area SR in the first chemical solution supply step, the substrate W is rotated to thereby apply the micro area SR to which hydrochloric acid is adhered. Nitric acid is supplied from the second nozzle 4 as the second chemical supply step. As a result, hydrochloric acid and nitric acid are mixed in the microregion SR, and the bevel etching solution is generated by the reaction of hydrochloric acid and nitric acid. Since the bevel etchant contains an etching component capable of dissolving platinum generated by the reaction of hydrochloric acid and nitric acid, that is, nitrosyl chloride, the bevel etchant is formed on the surface peripheral portion TR and the end surface portion of the substrate connected to the surface peripheral portion TR. The unnecessary thin film TF is dissolved in a bevel etchant and removed by etching. As described above, in the present embodiment, the supply of hydrochloric acid from the first nozzle 3 and the supply of nitric acid from the second nozzle 4 are repeatedly performed on the micro area SR, so that a bevel etching solution having corrosive properties in the micro area SR is obtained. Are generated and an etching process is performed.

  Further, even when the etching process is performed with a highly corrosive etching solution as in the present embodiment, the etching solution is generated on the substrate surface without being generated and held in advance in the substrate processing apparatus. This prevents corrosion of the parts of the apparatus by the etching solution. Furthermore, since hydrochloric acid and nitric acid are mixed on the surface peripheral portion TR of the substrate on which the thin film TF is to be removed, etching is performed with an etching solution having a high etching ability immediately after mixing, so that the etching can be efficiently removed. Done. Furthermore, according to this configuration, hydrochloric acid and nitric acid are directly supplied from the first and second nozzles 3 and 4 toward the surface peripheral portion TR of the substrate, so that hydrochloric acid and nitric acid are placed on the surface peripheral portion TR of the substrate. In this case, the reaction of hydrochloric acid and nitric acid is carried out efficiently, and a bevel etching solution sufficiently containing nitrosyl chloride as an etching component is generated. Thereby, the thin film TF can be efficiently removed by etching.

  Thus, when the etching process by the bevel etching process for a predetermined time is completed, the supply of hydrochloric acid and nitric acid is stopped simultaneously. Next, the DIW supply unit 17 is actuated, DIW is supplied from the first nozzle 3 and the second nozzle 4, and a rinsing process is performed on the surface peripheral portion TR and the end face of the substrate W (step S 7). When DIW is supplied from the first nozzle 3 and the second nozzle 4 for a predetermined time and the rinse process is completed, the supply of DIW is stopped simultaneously. Although the rinsing process may be executed by supplying DIW from either one of the first nozzle 3 or the second nozzle 4, the time required for the rinsing process is shortened by supplying DIW from both nozzles. Is done.

  After the rinsing process is completed, the first nozzle 3 is positioned from the supply position P31 to the standby position P32 (step S8). Similarly, the second nozzle 4 is also positioned from the supply position P41 to the standby position P42 (step S8).

  Subsequently, the facing member 5 is rotated in the same direction at substantially the same rotational speed as that of the spin base 15 (step S9). Thereafter, the processing liquid is supplied from the lower surface processing nozzle 2 to the back surface Wb of the rotating substrate W, and the back surface cleaning process is performed on the substrate back surface Wb (step S10). Specifically, the chemical solution supply unit 16 is operated, and the back surface etching solution is supplied from the bottom surface processing nozzle 2 toward the center of the substrate back surface Wb, whereby the substrate connected to the entire substrate back surface Wb and the back surface Wb. The end face portion is etched. Since the back surface etching solution is generated by diluting hydrochloric acid and nitric acid mixed in advance in the mixed solution tank 163 with DIW, it is substantially an etching component than the bevel etching solution generated on the front surface peripheral portion TR. The concentration of is adjusted low. A metal film containing platinum is attached to the back surface of the substrate W, but its film thickness is thinner than the thin film TF formed on the substrate surface Wf. Therefore, etching is sufficiently removed by supplying a back surface etching solution generated by diluting and mixing hydrochloric acid and nitric acid in advance. As described above, in this embodiment, since the etching solutions having different etching component concentrations corresponding to the film thickness of the metal film to be removed by etching are used, the chemical solution is used efficiently and the consumption of the chemical solution is reduced. Can be suppressed. After the back surface etching liquid is supplied from the bottom surface processing nozzle 2 for a predetermined time, the DIW supply unit 17 is operated, and DIW is supplied as the rinsing liquid for a predetermined time, so that the entire substrate back surface Wb and the substrate end surface portion connected to the back surface Wb are formed. Washed.

  Moreover, by rotating the opposing member 5 together with the substrate W, it is possible to prevent the processing liquid adhering to the opposing member 5 from adversely affecting the process. Further, it is possible to suppress the generation of an excessive air flow accompanying the rotation between the substrate W and the opposing member 5 and prevent the mist-like processing liquid from being caught on the substrate surface Wf.

  Here, by separating the support pins F1 to F6 and S1 to S6 from the substrate back surface Wb at least once during the back surface cleaning process, the support pins F1 to F6, S1 to S6 and the substrate back surface Wb are also brought into contact with each other. The treatment liquid can be circulated to clean the part. For example, support of both the first support pin group including the support pins F1 to F6 and the second support pin group including the support pins S1 to S6 is performed once during the supply process of the back surface etching liquid or the rinse liquid. The state in which the substrate W is supported by the pin group is switched to the state in which the substrate W is supported only by the first support pin group, and the processing liquid is introduced to the contact portion between the substrate W and the second support pin group. Then, after shifting to a state in which the substrate W is supported by both the support pin groups, the substrate W is switched to a state in which the substrate W is supported only by the second support pin group, and the contact between the substrate W and the first support pin group is changed. Allow the processing solution to wrap around the part. As a result, it is possible to perform the cleaning process on the entire back surface by causing the processing liquid to wrap around all of the contact portions between the substrate W and the support pins F1 to F6 and S1 to S6.

  Thus, when the back surface cleaning process is completed, the substrate W and the opposing member 5 are rotated at a high speed (for example, 1500 rpm). Thereby, drying of the substrate W is executed (step S11). At this time, the nitrogen gas is supplied from the gas supply path 23 together with the supply of the nitrogen gas to the substrate surface Wf, and the nitrogen gas is supplied to the front and back surfaces of the substrate W, thereby promoting the drying process of the substrate W.

  When the drying process of the substrate W is completed, the rotation of the opposing member 5 is stopped and simultaneously the rotation of the substrate W is stopped (step S12). Then, after the facing member 5 is raised (step 13), the supply of nitrogen gas from the gas supply path 57 and the gas discharge port 502 is stopped (step S14). As a result, the pressing and holding of the substrate W to the support pins F1 to F6 and S1 to S6 is released, and the processed substrate W is unloaded from the apparatus.

  As described above, according to this embodiment, hydrochloric acid and nitric acid are directly supplied toward the surface peripheral portion TR of the substrate W, and a bevel etching solution is generated on the surface peripheral portion TR. Thus, even when the etching process is performed with a highly corrosive etching solution, the etching solution is generated on the surface of the substrate without being generated and held in advance in the substrate processing apparatus. It is possible to prevent corrosion of the parts of the device due to the liquid. Furthermore, by mixing hydrochloric acid and nitric acid on the surface peripheral portion TR of the substrate, an etching process is performed with an etching solution having a high etching ability immediately after mixing. Moreover, since hydrochloric acid and nitric acid are sufficiently mixed on the surface peripheral portion of the substrate by supplying hydrochloric acid and nitric acid directly toward the surface peripheral portion TR of the substrate, the etching component (nitrosyl chloride) is sufficiently contained. The included bevel etchant is generated. Thereby, the metal film containing platinum adhering to the surface peripheral portion TR of the substrate is efficiently etched away by the bevel etchant, and the time required for the etching removal can be shortened.

  In addition, the metal film containing platinum that adheres to the back surface of the substrate is etched by the back surface etching solution that is generated by diluting and mixing hydrochloric acid and nitric acid in advance and has a substantially lower etching component concentration than the bevel etching solution. . As described above, by directly supplying hydrochloric acid and nitric acid to the surface peripheral portion TR of the substrate, the etching process is performed by the bevel etching solution generated on the surface peripheral portion TR of the substrate. In contrast, by performing etching with a back surface etching solution that is generated in advance and has a lower etching component concentration than the bevel etching solution, platinum adhering to the front surface peripheral portion TR and the back surface of the substrate is removed. The contained metal film is efficiently removed by etching. As described above, since the etching solutions having different concentrations of the etching components corresponding to the thickness of the metal film to be removed by etching are used, the chemical solution is used efficiently and the consumption of the chemical solution can be suppressed.

  Further, according to this embodiment, when the first and second nozzles 3 and 4 are positioned at the supply positions P31 and P41, the first and second nozzles 3 and 4 are connected to the nozzle insertion hole 5A of the facing member 5. , 5B. For this reason, the processing liquid is blocked by the lower surface 501 of the opposing member 5 even when the processing liquid scatters and bounces back toward the nozzles (first and second nozzles 3 and 4) during the etching process. Thereby, a large amount of processing liquid does not adhere to the nozzle. Therefore, it is possible to prevent the processing liquid from dropping from the nozzle and adhering to the substrate W or the substrate peripheral member when the nozzle is moved.

  In this embodiment, a holding member such as a chuck pin that holds the substrate W in contact with the outer peripheral end of the substrate W is not provided. Therefore, the processing liquid shaken off radially outward from the rotating substrate W does not hit the holding member and rebound to the substrate surface Wf. In addition, the holding member may be a factor that disturbs the airflow in the vicinity of the outer peripheral edge of the substrate W. However, since this factor does not exist, the mist-like processing liquid is less likely to be caught on the substrate surface Wf side. Further, in this embodiment, the nitrogen gas supplied from the gas supply path 57 and the gas discharge port 502 to the space SP sandwiched between the substrate surface Wf and the lower surface of the opposing member 5 leads to the non-process region NTR at the center of the surface. The entry of chemicals is prevented. Therefore, the metal film can be removed by etching uniformly over the entire circumference of the surface peripheral portion TR.

  In the above embodiment, the substrate processing apparatus is equipped with the first nozzle 3 and the second nozzle 4, but the number of nozzles is not limited to two. Even when three or more nozzles are provided, it is sufficient that there are at least one nozzle for supplying hydrochloric acid and one for supplying nitric acid.

Second Embodiment
FIG. 11 is a view showing the supply position P31 of the first nozzle 3 and the supply position P41 of the second nozzle 4 in the second embodiment of the substrate processing apparatus according to the present invention. The substrate processing apparatus according to the second embodiment is different from the first embodiment in the following points. That is, in the first embodiment, the supply position P31 of the first nozzle 3 and the supply position P41 of the second nozzle 4 extend from the rotation center A0 to the supply position P31 of the first nozzle 3 and the rotation center A0 in plan view. Whereas the angle formed by the direction extending to the supply position P41 of the second nozzle 4 is 180 °, in this embodiment, the supply position P31 of the first nozzle 3 and the supply position P41 of the second nozzle 4 are adjacent to each other. Are arranged to be. Specifically, the first nozzle 3 and the second nozzle 4 are arranged so that the distance between the discharge ports is about 15 mm. Further, the supply position P31 of the first nozzle 3 is arranged to be located downstream of the supply position P41 of the second nozzle 4 in the rotation direction R of the substrate W.

  The first and second nozzles 3 and 4 are attached in order of the second nozzle 4 and the first nozzle 3 from the free end side of the common nozzle arm AR, and the common nozzle movement connected to the nozzle arm AR is performed. By driving a mechanism (not shown), the mechanism can be moved integrally. By driving the nozzle moving mechanism, the first and second nozzles 3 and 4 are inserted into the nozzle insertion holes 5A and 5B of the facing member 5, respectively, and are positioned at the first supply position P31 and the second supply position P41. As described above, when the supply positions P31 and P41 of the first and second nozzles 3 and 4 are adjacent to each other, the first and second nozzles are made a common nozzle moving mechanism, thereby simplifying the apparatus configuration. Can do.

  In the apparatus having such a configuration, hydrochloric acid and nitric acid are continuously supplied from the first nozzle 3 and the second nozzle 4 to the surface peripheral portion TR of the rotating substrate W, respectively. Thereby, the thin film is etched and removed from the surface peripheral portion TR and the substrate end surface portion connected to the surface peripheral portion TR over the entire periphery. Thus, in this embodiment, since the supply position of hydrochloric acid and nitric acid is adjacent, hydrochloric acid and nitric acid can be mixed more efficiently. In addition, as shown in FIG. 11, after the nitric acid is supplied from the second nozzle 4 to the minute region SR, the substrate W rotates, so that the first nozzle 3 causes the minute region SR to which nitric acid is adhered. Hydrochloric acid is supplied. As a result, hydrochloric acid and nitric acid are mixed in the microregion SR, and the bevel etching solution is generated by the reaction of hydrochloric acid and nitric acid.

  In order to efficiently generate nitrosyl chloride (that is, an etching component) that dissolves by reacting with platinum by the reaction of the above (formula 1), as described above, a commercially available nitric acid stock solution (aqueous solution having a nitric acid concentration of 60%) And a hydrochloric acid stock solution (aqueous solution having a hydrochloric acid concentration of 35%) are preferably mixed in a volume ratio of nitric acid: hydrochloric acid = 1: 3. That is, the etching component is efficiently generated in a state where the proportion of hydrochloric acid is higher than that of nitric acid. According to this configuration, when hydrochloric acid and nitric acid are supplied toward the surface peripheral portion TR of the rotating substrate W, the hydrochloric acid supply position P31 is more downstream in the substrate rotation direction R than the nitric acid supply position P41. Therefore, when attention is paid to the minute region SR, nitric acid is first supplied, and hydrochloric acid is supplied after the nitric acid is attached. As a result, a part of the attached nitric acid is pushed away by hydrochloric acid and removed from the surface peripheral portion TR of the substrate W, and in the microregion SR of the surface peripheral portion TR of the substrate W after the hydrochloric acid is supplied, hydrochloric acid is removed. Therefore, the etching component, that is, nitrosyl chloride is efficiently generated in the bevel etchant. Therefore, the metal film containing platinum attached to the surface peripheral portion TR of the substrate W can be efficiently etched by the bevel etchant.

<Others>
The present invention is not limited to the above-described embodiment, and various modifications other than those described above can be made without departing from the spirit of the present invention.

  In the first embodiment, the angle formed by the direction extending from the rotation center A0 to the supply position P31 of the first nozzle 3 and the direction extending from the rotation center A0 to the supply position P41 of the second nozzle 4 in a plan view is 180 °. However, the angle is not limited to this, and may be set to any angle other than 180 °, such as 90 ° or 120 °. At this time, it is preferable that the supply position P31 of the first nozzle 3 is arranged downstream of the supply position P41 of the second nozzle 4 in the rotation direction of the substrate.

  As another modification, a heating unit that heats at least one of hydrochloric acid supplied to the first nozzle 3 and nitric acid supplied to the second nozzle 4 in the chemical solution supply unit 16 may be further provided. As a result, the temperature of the chemical solution supplied to the surface peripheral portion TR is increased, so that the speed of dissolving the metal film of the bevel etchant is increased, and the time required for the etching process with the bevel etchant can be further shortened.

  In the above embodiment, the first and second nozzles 3 and 4 are positioned in the nozzle insertion holes 5 </ b> A and 5 </ b> B formed in the facing member 5 when the first and second nozzles 3 and 4 are positioned at the supply position where the chemical liquid can be supplied to the surface peripheral portion TR. Although the first and second nozzles 3 and 4 are inserted, it is not always necessary to insert the first and second nozzles 3 and 4 into the nozzle insertion holes 5A and 5B. For example, a counter member having a plane size smaller than the plane size of the substrate W may be disposed opposite to the substrate surface Wf, and the first and second nozzles 3 and 4 may be disposed close to the side wall of the counter member.

  Also, with respect to the nozzle insertion holes of the opposing member 5, in the above-described embodiment, two nozzle insertion holes are formed in the opposing member 5 corresponding to the first and second nozzles 3, 4. A nozzle insertion hole may be formed.

  In the above embodiment, hydrochloric acid is used as the first chemical solution and nitric acid is used as the second chemical solution. However, for the treatment using the highly corrosive chemical solution generated by mixing other chemical solutions, The present invention can be applied.

  The present invention relates to a semiconductor wafer, a glass substrate for photomask, a glass substrate for liquid crystal display, a glass substrate for plasma display, a substrate for FED (Field Emission Display), a substrate for optical disk, a substrate for magnetic disk, a substrate for magneto-optical disk, etc. The present invention can be applied to a substrate processing apparatus and a substrate processing method for performing a bevel etching process on the surface of various substrates including a substrate.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows 1st Embodiment of the substrate processing apparatus concerning this invention. It is a block diagram which shows the main control structures of the substrate processing apparatus of FIG. It is the top view which looked at the spin base from the upper part. It is the elements on larger scale which show the structure of a support pin. It is a bottom view of an opposing member. It is a figure which shows the structure of the nozzle insertion hole provided in the 1st nozzle and the opposing member. It is a figure which shows a chemical | medical solution processing unit typically. It is sectional drawing for demonstrating the relationship between the outer diameter of a 1st and 2nd nozzle, and the hole diameter of a nozzle insertion hole. It is a flowchart which shows operation | movement of the substrate processing apparatus of FIG. It is a top view for demonstrating the etching removal effect | action of the thin film by a chemical | medical solution. It is a top view for demonstrating the etching removal effect | action of the thin film by the chemical | medical solution in 2nd Embodiment.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Spin chuck 3 ... 1st nozzle 4 ... 2nd nozzle 5 ... Opposing member 5A, 5B ... Nozzle insertion hole 15 ... Spin base 18 ... Gas supply unit 33 ... 1st nozzle moving mechanism 43 ... 2nd nozzle moving mechanism 501 ... Lower surface of facing member 502 ... Gas outlet A0 ... Rotation center of substrate (F1-F6) Support pin P31 ... Supply position P41 ... Supply position R ... Rotation direction of (substrate) S1-S6 ... Support pin SP ... (Substrate facing) Space between the surface and the substrate surface) TR ... front surface peripheral edge W ... substrate Wb ... substrate back surface Wf ... substrate surface

Claims (8)

A substrate holding means for holding the substrate with the surface of the substrate facing upward;
Rotating means for rotating the substrate held by the substrate holding means;
First chemical liquid supply means for supplying a first chemical liquid toward the peripheral edge of the surface of the substrate held by the substrate holding means;
Second chemical liquid supply means for supplying a second chemical liquid toward the peripheral edge of the surface of the substrate held by the substrate holding means;
With
The first chemical liquid and the second chemical liquid supplied from the first chemical liquid supply means and the second chemical liquid supply means are mixed on the peripheral edge of the surface of the substrate held by the substrate holding means and rotated by the rotating means. A substrate processing apparatus characterized in that a bevel etching solution having corrosivity is generated by etching, and an unnecessary material on a peripheral portion of the surface of the substrate is etched with the bevel etching solution.   A backside etching solution supply unit that supplies a backside etching solution generated by diluting and mixing the first chemical solution and the second chemical solution in advance toward the backside of the substrate held by the substrate holding unit. The substrate processing apparatus according to claim 1, wherein: The first chemical liquid supply means includes a first chemical liquid supply nozzle that supplies the first chemical liquid from the first supply position facing the surface peripheral edge of the substrate toward the surface peripheral edge of the substrate;
A first nozzle moving mechanism for moving the first chemical solution supply nozzle between the first supply position and a first standby position separated from above the substrate;
The second chemical liquid supply means supplies a second chemical liquid from a second supply position that is different from the first supply position and faces the surface peripheral edge of the substrate toward the surface peripheral edge of the substrate. A nozzle,
A second nozzle moving mechanism for moving the second chemical liquid supply nozzle between the second supply position and a second standby position away from above the substrate;
By disposing the first chemical liquid supply nozzle and the second chemical liquid supply nozzle at the first and second supply positions, respectively, and discharging the first chemical liquid and the second chemical liquid from the respective nozzles, the peripheral edge portion of the substrate surface is unnecessary. 3. The substrate processing apparatus according to claim 1, wherein the substrate is etched.   The first nozzle moving mechanism and the second nozzle moving mechanism are constituted by a common nozzle moving mechanism, and the first chemical liquid supply nozzle and the second chemical liquid supply nozzle move integrally. Item 4. The substrate processing apparatus according to Item 3. A plurality of nozzles that are arranged close to each other while facing the surface of the substrate held by the substrate holding means, and in which the first chemical solution supply nozzle and the second chemical solution supply nozzle are respectively inserted at positions facing the surface peripheral portion of the substrate. It further includes an opposing member in which an insertion hole is formed,
The first and second nozzle moving mechanisms insert the first chemical liquid supply nozzle and the second chemical liquid supply nozzle into the plurality of nozzle insertion holes, respectively, so that each nozzle is positioned at the first and second supply positions. 5. The substrate processing apparatus according to claim 3, wherein the substrate processing apparatus is characterized in that: The facing member has a substrate facing surface facing the surface of the substrate held by the substrate holding means, and a gas discharge port is formed on the substrate facing surface,
The substrate holding means is provided so as to be rotatable about a vertical axis, and protrudes upward from the rotating member. The substrate holding means abuts on the back surface of the substrate and supports the substrate apart from the rotating member. Having at least three or more support members, and a gas supply unit that presses the substrate against the support member by supplying gas from the gas discharge port to a space sandwiched between the substrate facing surface and the surface of the substrate. 6. The substrate processing apparatus according to claim 5, wherein:   The substrate processing apparatus according to claim 1, wherein the first chemical solution is hydrochloric acid and the second chemical solution is nitric acid. A substrate holding and rotating step of holding and rotating the substrate;
A first chemical solution supplying step that is performed in parallel with the substrate holding and rotating step and that supplies the first chemical solution toward the peripheral edge of the surface of the substrate;
A second chemical supply step that is performed in parallel with the substrate holding rotation step and the first chemical supply step, and supplies a second chemical toward the surface peripheral edge of the substrate;
Corrosive bevel etching generated by mixing the first chemical solution supplied in the first chemical solution supply step and the second chemical solution supplied in the second chemical solution supply step on the peripheral edge of the surface of the substrate. A substrate processing method comprising: a bevel etching step of etching an unnecessary material at a peripheral portion of the surface of the substrate with a liquid.

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