JP2011210933A - Substrate processing method and substrate processing apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To further enhance removal efficiency of particles or the like in a substrate processing method and apparatus for subjecting the substrate surface to physical cleaning in a state that a pattern is structurally reinforced by solidifying liquid entering gaps of the pattern.SOLUTION: A substrate W is held by a substrate holding means 11 and formed with a prescribed pattern FP while DIW as liquid is deposited on the surface Wf. HFE liquid as first processing liquid is supplied from a first processing-liquid supply means 25 to the surface Wf of the substrate W. The DIW liquid is removed from the substrate surface while leaving the DIW in the gaps of the pattern FP. A liquid film of the processing liquid is simultaneously formed on the substrate surface. Then, freezing nitrogen gas is ejected from a solidification means 31 to the substrate rear-surface Wb. The DIW left in the gaps of the pattern FP is solidified so as to form solidified bodies in the gaps of the pattern FP. In that state, a liquid film of DIW as second processing liquid is formed on the liquid film of the HFE liquid being the first processing liquid. Ultrasonic vibration is imparted to the DIW liquid film by an ultrasonic cleaning means 17 so as to execute cleaning.

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 method and a substrate processing apparatus for performing a cleaning process on various substrates (hereinafter simply referred to as “substrates”).

  The manufacturing process of an electronic component such as a semiconductor device or a liquid crystal display device includes a step of repeatedly forming a fine pattern by repeatedly performing processes such as film formation and etching on the surface of the substrate. Here, in order to perform fine processing satisfactorily, it is necessary to keep the substrate surface clean, and a cleaning process is performed on the substrate surface as necessary. For example, in the apparatus described in Patent Document 1, a fine pattern is structurally structured by freezing a liquid such as deionized water (hereinafter referred to as “DIW”) that has entered the gap between the fine patterns. Physical cleaning is performed on the substrate surface in a state of being reinforced.

  That is, in the apparatus described in Patent Document 1, the following steps are executed. First, DIW is supplied to the surface of the substrate so that DIW enters the pattern gap and a liquid film of DIW is formed on the entire surface of the substrate. Subsequently, the supply of DIW is stopped and the number of rotations of the substrate is controlled to remove DIW from the substrate surface while the DIW that has entered the pattern gap remains. Then, the DIW remaining inside the pattern gap is frozen to form ice, and the pattern is structurally reinforced. Thereafter, physical cleaning is performed on the substrate surface while the ice inside the pattern gap is kept frozen. Accordingly, contaminants such as particles can be efficiently removed from the substrate surface while preventing the pattern from being damaged.

JP 2008-243981 (FIG. 6)

  In the above prior art, the substrate on which the DIW liquid film is formed is rotated to remove the DIW from the substrate surface while leaving the DIW inside the pattern gap. A DIW liquid film may remain on the upper surface of the pattern. In this case, if contaminants such as particles (hereinafter referred to as “particles”) are present on the upper surface of the pattern where the liquid film remains, the liquid film on the upper surface of the pattern is also frozen when the solidified body is formed. Etc. are buried in the DIW solidified body (frozen film).

  Even if the DIW on the upper surface of the pattern can be removed, the substrate temperature is subsequently cooled to 0 ° C. (degrees Celsius) or lower when the solidified body is formed. Adhere to. For this reason, if particles or the like remain on the substrate surface, the particles or the like are buried in frost.

  In these cases, even if the substrate surface is subsequently subjected to physical cleaning, it is difficult to clean and remove the DIW solidified body on the upper surface of the pattern or the particles buried in the frost adhering to the substrate surface. Thus, there was room for improvement from the viewpoint of particle removal efficiency.

  The present invention has been made in view of the above problems, and in a substrate processing method and apparatus for structurally reinforcing a pattern by solidifying a liquid that has entered the gap between patterns and physically cleaning the substrate surface, particles and the like The purpose is to further improve the removal efficiency.

  In order to solve the above problem, the present invention provides a solidification step of forming a liquid solidified body inside a gap between patterns of a substrate on which a predetermined pattern is formed, and holding a liquid film on the surface of the substrate, and a gap between the patterns. An ultrasonic cleaning step of cleaning the substrate surface by applying ultrasonic vibration to the substrate through a liquid film held on the substrate surface while maintaining a state in which a solidified body is formed inside.

  Moreover, this invention can contain the process liquid which has a freezing point lower than the freezing point of a liquid which is hard to mix with a liquid as a liquid film.

  Further, according to the present invention, prior to the solidification step, a processing liquid for forming a liquid film is supplied to the surface of the substrate on which the pattern is formed and the liquid adheres, and the liquid is left while the liquid remains inside the gap of the pattern. A laminated liquid film forming step is also provided for removing from the substrate surface and forming a liquid film of the treatment liquid on the upper layer of the liquid inside the pattern gap.

  The present invention also provides a substrate holding means for holding a substrate on which a predetermined pattern is formed and a liquid is attached, a substrate rotating means for rotating the substrate, and a processing liquid toward the surface of the substrate held by the substrate holding means. A laminated liquid film forming means for supplying and removing the liquid from the substrate surface while leaving the liquid inside the pattern gap, and forming a liquid film of the treatment liquid on the upper layer of the liquid inside the pattern gap; and a liquid film of the treatment liquid And solidifying the liquid remaining inside the pattern gap to form a solidified body inside the pattern gap, while maintaining the state where the solidified body is formed inside the pattern gap, Ultrasonic cleaning means for cleaning the substrate surface by applying ultrasonic vibration to the substrate through the formed liquid film is provided.

  In the invention (substrate processing method and apparatus) configured as described above, by supplying the processing liquid to the substrate surface, the liquid adhering to the substrate surface while the liquid remains inside the gaps of the pattern formed on the substrate surface. The processing liquid removed from the substrate surface and used for removing the liquid forms a liquid film of the processing liquid on the substrate surface. As a result, the liquid is removed from the substrate surface including the upper surface of the pattern except the inside of the pattern gap. In this state, the liquid remaining in the pattern gap is solidified to form a solidified body in the pattern gap, so that no liquid solidified body is formed on the upper surface of the pattern.

  Further, the liquid film of the treatment liquid is maintained even after the liquid solidified body is formed, and ultrasonic waves are applied to the liquid film of the treatment liquid. For this reason, the substrate surface is shielded from the atmosphere by the liquid film of the processing liquid, and frost does not adhere to the substrate surface. For this reason, it becomes possible to wash | clean the pattern upper surface and the board | substrate surface in which the pattern is not formed favorably.

  Further, by forming a liquid solidified body inside the pattern gap, the pattern is structurally reinforced. That is, it can be regarded as a lump (solid material) in which the pattern and the solidified body are integrated. Since the substrate surface is cleaned by applying an ultrasonic wave while maintaining a solidified body (solidified state), particles are efficiently removed from the substrate surface while preventing the pattern from being damaged. Can be removed.

  In addition, since the liquid and the processing liquid are difficult to mix with each other, the processing liquid does not enter the pattern gap even if the liquid in the upper layer of the substrate is removed, and the liquid inside the pattern gap is not excluded. Moreover, the change of the freezing point of the liquid is not caused by mixing the treatment liquid with the liquid.

  In addition, by using a processing liquid having a freezing point lower than the freezing point of the liquid, when the liquid inside the pattern gap is solidified, the liquid is cooled to a temperature higher than the freezing point of the processing liquid and lower than the freezing point of the liquid. It is possible to solidify only the liquid and leave the treatment liquid unsolidified, and then apply ultrasonic waves to the treatment liquid to clean the substrate, and then treat the treatment liquid mixed with particles after the ultrasonic cleaning to the substrate. It becomes possible to exclude from above.

  Here, the processing liquid includes at least a first processing liquid having a temperature higher than the freezing point of the liquid, and the laminated liquid film forming step includes a first processing liquid supply step for supplying the first processing liquid. Is possible.

  In the invention configured as described above, by supplying the first processing liquid having a temperature higher than the freezing point of the liquid, the liquid is not solidified before the liquid other than the inside of the pattern gap is excluded. No coagulum remains.

  The laminated liquid film forming step may further include a step of rotating the substrate and supply the first processing liquid to the vicinity of the center of the substrate.

  In the invention configured as described above, by supplying the first processing liquid to the vicinity of the center of the substrate while rotating the substrate, a centrifugal force is applied to the first processing liquid from the center of the substrate toward the periphery of the substrate. The liquid can be sequentially removed toward the periphery of the substrate. Thereby, the amount of the first processing liquid to be used can be reduced as compared with the case where the first processing liquid is supplied onto the stationary substrate, and the time required for performing the laminated liquid film forming process can be shortened. It becomes possible.

  The first treatment liquid supply step may be configured to supply a first treatment liquid having a temperature near the freezing point of the liquid.

  In the invention configured as described above, it is possible to form a liquid solidified body in a short time in the solidification step without increasing the temperature of the liquid inside the pattern gap.

  According to the present invention, the processing liquid is supplied to the substrate surface on which the pattern is formed to exclude the liquid from the substrate surface excluding the inside of the pattern gap, and the processing liquid forms a liquid film on the substrate surface as it is. As a result, the liquid can be isolated and remain only in the gaps of the pattern, and even if the liquid solidified body is formed thereafter, the liquid solidified body is not formed on the upper surface of the pattern. Further, by continuously holding the liquid film of the processing liquid on the substrate surface, frost does not adhere to the substrate surface even if a liquid solidified body is formed and then ultrasonic cleaning is performed. For this reason, particles on the upper surface of the pattern, which were difficult in the prior art, can be removed by washing, and the washing efficiency can be further improved.

It is a top view which shows schematic structure of the substrate processing apparatus which concerns on this invention. It is a front view which shows schematic structure of the substrate processing apparatus which concerns on this invention. It is a figure which shows schematic structure of the processing unit which concerns on 1st embodiment. It is front sectional drawing which shows the structure of the ultrasonic cleaning head used with the processing unit of FIG. It is a flowchart which shows operation | movement of the substrate processing apparatus which concerns on 1st embodiment. It is a schematic diagram which shows the state by which the liquid was supplied to the substrate surface in 1st embodiment. It is a schematic diagram which shows the state from which the liquid was removed with the 1st process liquid in 1st embodiment. It is a schematic diagram which shows the state by which the liquid was solidified in 1st embodiment. It is a schematic diagram which shows the state in which the thickness of the liquid film of the 1st process liquid was adjusted in 1st embodiment. It is a schematic diagram which shows the state in which the liquid film of the 2nd process liquid was formed on the liquid film of the 1st process liquid in 1st embodiment. It is a schematic diagram which shows the state by which the ultrasonic wave is provided to the 2nd process liquid in 1st embodiment. It is a schematic diagram which shows the state in which cleaning by SC1 is performed in 1st embodiment. It is a schematic diagram which shows the state in which the rinse process is performed in 1st embodiment. It is a figure which shows schematic structure of the processing unit which concerns on 2nd embodiment. It is a flowchart which shows operation | movement of the substrate processing apparatus concerning 2nd embodiment. It is a schematic diagram which shows the state by which the liquid was solidified with the 2nd process liquid in 2nd embodiment. It is front sectional drawing which shows the structure of the ultrasonic cleaning nozzle used by 3rd embodiment. It is a flowchart which shows operation | movement of the substrate processing apparatus concerning 3rd embodiment.

  In the following description, a substrate means 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, and a magneto-optical substrate. Various substrates such as disk substrates.

  In the following description, the surface of the substrate on which various patterns such as circuit patterns are formed is referred to as the front surface, and the opposite surface is referred to as the back surface. Further, the surface of the substrate directed downward is referred to as a lower surface, and the surface of the substrate directed upward is referred to as an upper surface.

  Embodiments of the present invention will be described below with reference to the drawings, taking as an example a substrate processing apparatus used for processing a semiconductor wafer as an example of a substrate. However, the present invention can be applied not only to processing of semiconductor wafers but also to processing of various substrates such as glass substrates for liquid crystal displays. In addition, the substrate processing apparatus to which the present invention can be applied is not limited to the apparatus that performs the chemical treatment, the cleaning process, and the drying process continuously in the same apparatus, the apparatus that performs only a single process, the chemical process, and the cleaning process. The present invention can also be applied to a case where a part of the treatment and the drying treatment are continuously performed in the same apparatus.

<First embodiment>
1 and 2 are diagrams showing a schematic configuration of a substrate processing apparatus 91 according to the present invention. FIG. 1 is a plan view of the substrate processing apparatus 91, and FIG. 2 is a front view of the substrate processing apparatus 91 of FIG. 1 viewed from the direction of arrow X1. This apparatus is a cleaning process for removing contaminants such as particles (hereinafter referred to as “particles”) adhering to the surface of a substrate W such as a semiconductor wafer (hereinafter simply referred to as “substrate W”). 1 is a single-wafer type substrate processing apparatus.

  In the substrate processing apparatus 91, a transfer apparatus 5 that carries the substrate W into and out of the processing unit 1 is disposed at one end. A cassette station 7 is provided at one end of the transfer device 5 so that a cassette 8 that accommodates the substrate W can be placed thereon. On the side of the cassette station 7, a substrate before the processing step from the cassette 8 is provided. A substrate transfer device 51 including a transfer arm 511 for taking out W one by one and storing the processed substrates W one by one in the cassette 8 is provided.

  The placement unit 71 of the cassette station 7 is configured to be able to place a cassette 8 containing, for example, 25 substrates W. The substrate transfer device 51 is configured to be movable in the horizontal and vertical directions and to be rotatable about a vertical axis.

  Next, the configuration of the processing unit 1 will be described. FIG. 3 is a schematic diagram showing the configuration of the processing unit 1. The processing unit 1 includes a substrate holding unit 11, a substrate rotating unit 12, a processing cup 13, a blocking member 15, an ultrasonic cleaning unit 17, a liquid supply unit 21, a rinse liquid supply unit 23, One treatment liquid supply means 25, second treatment liquid supply means 22, SC1 supply means 29, coagulation means 31, drying gas supply means 33, and control unit 93 are provided.

  The substrate holding unit 11 holds the surface Wf of the substrate W in a substantially horizontal posture with the surface Wf facing upward. The substrate rotating unit 12 rotates the substrate holding unit 11 together with the substrate W held by the substrate holding unit 11. The processing cup 13 accommodates the substrate holding means 11 on the inside thereof, receives the scattered matter from the substrate holding means 11 and the substrate W, and exhausts / drains. The blocking member 15 is disposed above the substrate holding unit 11 so as to face the surface Wf of the substrate W held by the substrate holding unit 11 and blocks the substrate surface Wf from the outside air. The ultrasonic cleaning means 17 applies ultrasonic waves to the processing liquid supplied to the substrate surface Wf.

  The liquid supply means 21 supplies liquid to the substrate surface Wf. The rinse liquid supply means 23 supplies a rinse liquid to the substrate surface Wf. The first processing liquid supply means 25 supplies the first processing liquid to the substrate surface Wf and removes the liquid adhering to the substrate surface Wf. The second processing liquid supply means 22 supplies a mist-like second processing liquid on the liquid film of the first processing liquid supplied to the substrate surface Wf. The SC1 supply means supplies SC1 to the substrate surface Wf.

  The solidifying means 31 discharges a coolant from the back side of the substrate W to the back side Wb of the substrate W to form a liquid solidified body. The drying gas supply means 33 supplies a drying gas to the substrate surface Wf.

  The control unit 93 controls the operation of each part of the substrate processing apparatus 91 based on a cleaning program described later.

  The substrate holding unit 11 includes a central shaft 111, a spin base 113, a chuck pin 115, and a chuck pin driving mechanism 116.

  A disc-shaped spin base 113 having an opening at the center is fixed to the upper end of the center shaft 111 of the substrate holding means 11 by a fastening component such as a screw. Near the periphery of the spin base 113, a plurality of chuck pins 115 for holding the periphery of the substrate W are provided upright. Three or more chuck pins 115 may be provided to securely hold the circular substrate W, and are arranged at equiangular intervals along the peripheral edge of the spin base 113. Each of the chuck pins 115 includes a substrate support portion that supports the peripheral portion of the substrate W from below, and a substrate holding portion that holds the substrate W by pressing the outer peripheral end surface of the substrate W supported by the substrate support portion. ing.

  Each chuck pin 115 is connected to an air cylinder in the chuck pin driving mechanism 116 through a known link mechanism, a swinging member, or the like. When the air cylinder expands and contracts according to an operation command from the control unit 93, each chuck pin 115 is in a pressed state in which the substrate holding portion presses the outer peripheral end surface of the substrate W, and the substrate holding portion is moved from the outer peripheral end surface of the substrate W. It is configured to be switchable between a released state and a separated state. In this embodiment, an air cylinder is used as a drive source for the chuck pin 115, but a drive source such as a motor or a solenoid can also be used.

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

  Further, the rotation shaft of the substrate rotation means 12 including a motor is connected to the central shaft 111 of the substrate holding means 11. When the substrate rotating means 12 is driven by an operation command from the control unit 93, the spin base 113 fixed to the central shaft 111 rotates around the rotation center A0.

  The processing cup 13 is for collecting processing liquid and the like after being used for processing the substrate W, so that the processing liquid and the like scattered from the spin base 113, the chuck pins 115, and the substrate W can be received. It has a substantially cylindrical shape. In addition, an opening 131 through which the substrate W passes is formed on the upper surface. The opening 131 is substantially circular with the rotation center A0 as the center. An exhaust liquid line (not shown) is connected to the bottom of the processing cup 13 to exhaust (exhaust liquid) the atmosphere around the substrate holding unit 11 together with fine particles such as processing liquid contained therein.

  The blocking member 15 is formed in a disk shape having an opening at the center. The lower surface of the blocking member 15 is a substrate facing surface that faces the surface Wf of the substrate W substantially in parallel and is formed to have a size equal to or larger than the diameter of the substrate W. The blocking member 15 is attached substantially horizontally to the lower end portion of the support shaft 151 having a substantially cylindrical shape. The support shaft 151 is held by an arm 152 extending in the horizontal direction.

  In addition, the arm 152 is connected to a blocking member lifting mechanism 153, and the blocking member 15 is brought close to the spin base 113 and separated from the spin base 113 in response to an operation command from the control unit 93. Specifically, the control unit 93 controls the operation of the blocking member elevating mechanism 153 so that when the substrate W is loaded into and unloaded from the processing unit 1, the blocking member 15 is separated from the substrate holding unit 11. While the substrate W is raised (position shown in FIG. 3), the surface of the substrate W held by the substrate holding means 11 when the DIW or HFE liquid to be described later is supplied to the substrate W. Lower to an opposing position set very close to Wf.

  The blocking member 15 is connected to the blocking member rotating mechanism 155 and is rotated around a vertical axis passing through the center of the support shaft 151 by an operation command from the control unit 93. The blocking member rotating mechanism 155 is configured to rotate the blocking member 15 in the same rotation direction as the substrate W and at substantially the same rotation speed in accordance with the rotation of the substrate W held by the substrate holding unit 11.

  The support shaft 151 is hollow, and a first supply pipe 157 is inserted through the support shaft 151 and a second supply pipe 158 is inserted through the first supply pipe 157 to form a so-called double tube structure. . Lower end portions of the first supply pipe 157 and the second supply pipe 158 extend to the opening of the blocking member 15, and a discharge nozzle 159 is provided at the tip of the second supply pipe 158.

  A drying nitrogen gas supply unit 331 that supplies nitrogen gas at room temperature is connected to the first supply pipe 157 via a pipe 333.

  A main pipe 20 is connected to the second supply pipe 158, and the first DIW supply section 211, the second DIW supply section 231 and the main pipe 20 are connected to the second supply pipe 158 via pipes 213, 233, 253, and 293, respectively. The HFE liquid supply unit 251 and the SC1 supply unit 291 are each connected by a pipe line. In addition, on-off valves 215, 235, 255, and 295 are inserted in the pipes 213, 233, 253, and 293, respectively. Note that the on-off valves 215, 235, 255 and 295 are all normally closed.

  The ultrasonic cleaning means 17 includes an ultrasonic cleaning unit 171, a wiring 175, and an ultrasonic oscillator 173.

  A head drive mechanism 173 is provided on the outer side in the circumferential direction of the processing cup 13 as a drive source for moving the ultrasonic cleaning unit 171 up and down and turning. The head driving mechanism 173 has a lifting motor 1731, and a ball screw 1732 is connected to the rotating shaft of the lifting motor 1731. The ball screw 1732 is provided along with a standing guide 1733. The elevating base 1735 is slidably fitted to the guide 1733 and is screwed to the ball screw 1732. When the lifting motor 1731 is driven by an operation command from the control unit 93, the lifting base 1735 is lifted up and down.

  A swing motor 1736 is mounted on the elevating base 1735, and a swing shaft 1737 is connected to a rotation shaft of the swing motor 1736. One end of an arm 1713 is connected to the turning shaft 1737, and an ultrasonic cleaning head 1715 is held at the other end of the arm 1713. When the turning motor 1736 is driven by an operation command from the control unit 93, the arm 1713 swings around the turning shaft 1737 and the vicinity of the substrate surface Wf where the ultrasonic cleaning head 1715 is held on the substrate holding means 11. And a reciprocating motion between a retreat position which is a position deviated to the outer side in the circumferential direction of the processing cup 13.

  FIG. 4 is a cross-sectional view showing the configuration of the ultrasonic cleaning head 1715. The ultrasonic cleaning head 1715 has a diaphragm 1715b attached to a bottom side opening of a main body portion 1715a made of a fluororesin such as, for example, polytetrafluoroethylene. The diaphragm 1715b has a disk shape in plan view, and its bottom surface is a vibration surface VF. A vibrator 1715c is attached to the upper surface of the diaphragm 1715b. The vibrator 1715 c is electrically connected to the ultrasonic oscillator 173 through the wiring 175. Then, when a pulse signal is output from the ultrasonic oscillator 173 to the vibrator 1715c via the wiring 175 in accordance with an operation command from the control unit 93, the vibrator 1715c vibrates ultrasonically and vibrates the diaphragm 1715b. .

  When the ultrasonic cleaning head 1715 is positioned at the vibration applying position by the head driving mechanism 173, the interval between the vibration surface VF and the substrate surface Wf is controlled with high accuracy by driving control of the lifting motor 1731.

  Returning to FIG. The liquid supply unit 21 includes a first DIW supply unit 211, an on-off valve 215, a pipe 213, a main pipe 20, a second supply pipe 158, and a discharge nozzle 159.

  When the on-off valve 215 is opened by an operation command from the control unit 93, deionized water (De Ionized Water; hereinafter referred to as “DIW”) as a liquid is supplied from the first DIW supply unit 211 to the pipe 213, the main pipe 20, and the first pipe 20. It is supplied from the discharge nozzle 159 to the substrate surface Wf through the two supply pipes 158.

  The rinse liquid supply means 23 includes a second DIW supply unit 231, an on-off valve 235, a pipe 233, a main pipe 20, a second supply pipe 158, and a discharge nozzle 159.

  When the on-off valve 235 is opened by an operation command from the control unit 93, DIW as the rinsing liquid from the second DIW supply unit 231 passes from the discharge nozzle 159 to the substrate surface Wf through the pipe 233, the main pipe 20, and the second supply pipe 158. Supplied.

  Here, the first DIW supply unit 211 supplies DIW whose temperature is adjusted to, for example, 1 ° C. (degrees Celsius) in a DIW supply process and a DIW mist supply process described later. Further, the second DIW supply unit 231 supplies DIW whose temperature is adjusted to, for example, 40 ° C. (degrees Celsius) in order to defrost and remove the DIW solidified body remaining on the substrate surface Wf in the rinsing process described later. is there.

  The first processing liquid supply unit 25 includes an HFE liquid supply unit 251, an on-off valve 255, a pipe 253, a main pipe 20, a second supply pipe 158, and a discharge nozzle 159.

  When the on-off valve 255 is opened by an operation command from the control unit 93, the HFE liquid as the first processing liquid is supplied from the HFE liquid supply unit 251 from the discharge nozzle 159 through the pipe 253, the main pipe 20, and the second supply pipe 158. Supplied to the substrate surface Wf.

Here, the HFE liquid refers to a liquid mainly composed of hydrofluoroether. As the “HFE liquid”, for example, HFE of the trade name Novec (registered trademark) series manufactured by Sumitomo 3M Limited can be used. Specifically, as HFE, for example, chemical formula: C ₄ F ₉ OCH ₃ , chemical formula: C ₄ F ₉ OC ₂ H ₅ , chemical formula: C ₆ F ₁₃ OCH ₃ , chemical formula: C ₃ HF ₆ —CH (CH ₃ ) _O-C 3 HF _6, the _formula: such as C ₂ HF 4 OCH ₃ can be used. The density of these HFE liquids is 1430-1660 (kg / m ³ ), and the specific gravity with respect to water is greater than “1”. Accordingly, the DIW used as the “second processing liquid” in the present embodiment has a specific gravity smaller than the HFE liquid used as the “first processing liquid” in the present embodiment.

  Moreover, since all the HFE liquids represented by the respective chemical formulas have a freezing point of − (minus) 38 ° C. (Celsius) or lower, the freezing point is lower than the freezing point (0 ° C. (Celsius)) of DIW as a liquid.

  The second processing liquid supply unit 22 includes a first nozzle unit 19, a pipe 223, an on-off valve 225, and a first DIW supply unit 211.

  A nozzle driving mechanism 191 is provided on the outer side in the circumferential direction of the processing cup 13 as a driving source for scanning the first nozzle portion 19. A rotation shaft 193 is connected to the nozzle drive mechanism 191, and an arm 195 is connected to the rotation shaft 193 so as to extend in the horizontal direction. A mist supply nozzle 197 is attached to the tip of the arm 195. When the nozzle drive mechanism 191 is driven by an operation command from the control unit 93, the arm 195 is a position where the arm 195 is deviated from the discharge position above the substrate surface Wf and the outer side in the circumferential direction of the processing cup 13 around the rotation shaft 193. It swings between the retracted positions.

  The first nozzle unit 19 is connected to the first DIW supply unit 211 via a pipe 223. In addition, an on-off valve 225 is inserted in the pipe 223. The on-off valve 225 is normally closed, and the on-off valve 225 is opened by an operation command from the control unit 93 when DIW mist is supplied to the substrate surface Wf as described later. Thereby, DIW is pumped from the first DIW supply unit 211 to the first nozzle unit 19 via the pipe 223, and mist-like DIW is discharged from the mist supply nozzle 197 toward the substrate surface Wf.

  In addition, the laminated liquid film forming unit in the first embodiment includes a first processing liquid supply unit 25 and a second processing liquid supply unit 22.

  The SC1 supply unit 29 includes an SC1 supply unit 291, an on-off valve 295, a pipe 293, a main pipe 20, a second supply pipe 158, and a discharge nozzle 159.

  When the on-off valve 295 is opened by an operation command from the control unit 93, SC1 is supplied from the SC1 supply unit 291 to the substrate surface Wf from the discharge nozzle 159 via the pipe 293, the main pipe 20, and the second supply pipe 158.

Here, SC1 (Standard Clean 1) is ammonia (chemical formula: NH ₄ OH), hydrogen peroxide (chemical formula: H ₂ O ₂ ), and water (chemical formula: H ₂ O) in a volume ratio of 1: 1: 50, for example. A mixed aqueous solution.

  The coagulation means 31 includes a freezing nitrogen gas supply unit 311, a pipe 313, a gas supply pipe 117, and a discharge nozzle 119.

  The central axis 111 of the substrate holding means 11 is hollow, and a gas supply pipe 117 is inserted through the center axis 111. The gas supply pipe 117 is connected to the freezing nitrogen gas supply unit 311 via a pipe 313. An opening is provided at the center of the spin base 113, an upper end portion of the gas supply pipe 117 extends to the opening of the spin base 113, and a discharge nozzle 119 is provided at the tip of the gas supply pipe 117. . According to an operation command from the control unit 93, the freezing nitrogen gas supply unit 311 has a temperature lower than the freezing point of DIW and higher than the freezing point of the HFE liquid, for example, nitrogen gas at − (minus) 20 ° C. (Celsius). Is supplied from the discharge nozzle 119 to the substrate back surface Wb through the pipe 313 and the gas supply pipe 117.

  The drying gas supply means 33 includes a drying nitrogen gas supply unit 331, a pipe 333, and a first supply pipe 157.

  The drying nitrogen gas supply unit 331 is connected to the first supply pipe 157 via a pipe 333. The drying nitrogen gas supply unit 331 supplies room temperature nitrogen gas to the substrate surface Wf via the pipe 333 and the first supply pipe 157 in accordance with an operation command from the control unit 93.

  The control unit 93 stores in advance cleaning conditions corresponding to the substrate W as a cleaning program (also called a recipe), and controls each part of the substrate processing apparatus 91 according to the contents of the cleaning program. The control unit 93 is connected to an operation unit (not shown) used for creating / changing a cleaning program and selecting a desired one from a plurality of cleaning programs.

  Next, a cleaning process operation in the substrate processing apparatus 91 configured as described above will be described with reference to FIGS. FIG. 5 is a flowchart showing the operation of the processing unit 1 of FIG. 6 to 13 are schematic diagrams for explaining the operation of the processing unit 1 of FIG.

  Unless otherwise specified in the following description, the blocking member rotating mechanism 155 rotates the blocking member 15 at the same rotational speed in the direction in which the substrate rotating unit 12 rotates the substrate holding unit 11.

  First, a cleaning program corresponding to a predetermined substrate W is selected by an operation unit (not shown) and instructed to be executed. In preparation for carrying the substrate W into the processing unit 1, the following operation is performed according to an operation command from the control unit 93.

  That is, the blocking member rotating mechanism 155 stops the rotation of the blocking member 15, and the substrate rotating unit 12 stops the rotation of the substrate holding unit 11. The blocking member elevating mechanism 153 moves the blocking member 15 to the separated position shown in FIG. 3, and the substrate rotating unit 12 positions the substrate holding unit 11 to a position suitable for delivery of the substrate W. After the substrate holding unit 11 is positioned at a position suitable for delivery of the substrate W, the chuck pin driving mechanism 116 brings the chuck pin 115 into a released state.

  In addition, the first nozzle unit 19 is the mist supply nozzle 197, the ultrasonic cleaning unit 171 is the ultrasonic cleaning head 1715, and the retreat position (the mist supply nozzle 197 and the ultrasonic cleaning head 1715 are outside the processing cup 13 in the circumferential direction). Move to a position that is off. Furthermore, the on-off valves 215, 225, 235, 255 and 295 are closed, and the freezing nitrogen gas supply unit 311 and the drying nitrogen gas supply unit 331 stop supplying the freezing nitrogen gas and the drying nitrogen gas, respectively. Further, the ultrasonic oscillator 173 stops the ultrasonic oscillation.

  When the preparation for loading the substrate W into the processing unit 1 is completed, the substrate transport device 51 takes out the substrate W from a predetermined position of the cassette 8 placed on the placement unit 71 according to an operation command from the control unit 93, and performs processing. It carries in to the unit 1 (step S101).

  When an unprocessed substrate W is loaded into the processing unit 1 and placed on the substrate support portion of the chuck pin 115, the chuck pin driving mechanism 116 is chucked by an operation command from the control unit 93 to the substrate holding means 11. The pin 115 is pressed.

  When the unprocessed substrate W is held by the substrate holding means 11, the blocking member lifting mechanism 153 is lowered to the close position by the operation command from the control unit 93 and is positioned close to the substrate surface Wf. Then, according to the operation command of the control unit 93, the substrate rotating unit 12 starts rotating the substrate holding unit 11 at, for example, 100 rpm, and the rotation at the rotation number is continued. Further, the on-off valve 215 is opened by an operation command from the control unit 93 to the liquid supply means 21. Accordingly, DIW as a liquid is supplied from the first DIW supply unit 211 to the substrate surface Wf from the discharge nozzle 159 through the pipe 213, the main pipe 20, and the second supply pipe 158.

  The DIW supplied to the substrate surface Wf spreads uniformly over the entire surface of the substrate surface Wf due to the centrifugal force accompanying the rotation of the substrate W, and forms a DIW film (water film) that is a liquid on the substrate surface Wf. At this time, DIW enters the pattern gap due to the flow of DIW (liquid supply step) (step S102). The rotation speed of the substrate W is set so that the DIW on the substrate surface Wf flows and the DIW enters into the gaps of the pattern. FIG. 6 schematically shows a state in which a DIW liquid film F01 as a liquid is formed on the substrate surface Wf, and the DIW has penetrated into the gaps of the pattern FP.

  In the present embodiment, it is preferable to use DIW whose temperature is adjusted to about 0 to 2 ° C. (Celsius). This is because the temperature of the DIW liquid film F01 is relatively high, so that the DIW liquid film F01 evaporates before the DIW is removed by the HFE liquid so that the pattern FP is not collapsed. This is to shorten the time required for solidifying the DIW.

  Subsequently, the on-off valve 215 is closed by an operation command from the control unit 93 to the liquid supply means 21. Further, the on-off valve 255 is opened by an operation command from the control unit 93 to the first processing liquid supply means 25. Accordingly, the HFE liquid as the first processing liquid is supplied from the discharge nozzle 159 to the substrate surface Wf via the pipe 253, the main pipe 20, and the second supply pipe 158 from the HFE liquid supply unit 251. The substrate holding means 11 continues to rotate at the same rotational speed as in the liquid supply process (step S102).

  When the HFE liquid is supplied while rotating the substrate W held by the substrate holding means 11, DIW constituting the liquid film F01 is pushed out of the substrate W from the substrate surface Wf, and DIW is HFE on the entire substrate surface Wf. Replaced with liquid. However, the pattern FP formed on the substrate W such as a semiconductor wafer is fine, and the HFE liquid cannot easily enter the gap between the patterns FP. Further, since the HFE liquid is difficult to mix with DIW, it is further difficult to enter. That is, even if the DIW in the upper layer of the substrate surface Wf is excluded, the HFE liquid does not enter the gap of the pattern FP and does not exclude the DIW in the gap of the pattern FP. Further, the HFE solution is not mixed with DIW to cause a change in the freezing point of DIW.

  Therefore, a liquid film of the HFE liquid is formed on the liquid layer of DIW inside the gap of the pattern FP with the DIW remaining only inside the gap of the pattern FP (first processing liquid supply step) (step S103). ). FIG. 7 schematically shows a state in which DIW other than the inside of the gap of the pattern FP is removed by the HFE liquid, and the liquid film F03 of the HFE liquid as the first processing liquid is held on the substrate surface Wf.

  The temperature of the HFE liquid that replaces DIW on the substrate surface Wf is preferably adjusted to about 0 to 2 ° C. (Celsius). Because, if the temperature of the HFE liquid is high in the state where the DIW on the substrate surface Wf is replaced with the HFE liquid, the heat from the HFE liquid is conducted to the DIW remaining on the substrate surface Wf and the temperature of the DIW rises. This is because it takes time to form a DIW solidified body to be described later.

  After the liquid film F03 of the HFE liquid is formed on the entire substrate surface Wf of the upper layer of the pattern FP, and DIW other than the inside of the gap of the pattern FP on the substrate surface Wf is removed, the first processing liquid supply means 25 from the control unit 93 The on / off valve 255 is closed by the operation command to, and the supply of the HFE liquid to the substrate surface Wf is stopped. Thereafter, in accordance with an operation command from the control unit 93 to the coagulation means 31, the freezing nitrogen gas supply unit 311 starts supplying the freezing nitrogen gas. The substrate holding means 11 continues to rotate at the same rotational speed as in the first processing liquid supply step (step S103).

  The freezing nitrogen gas supplied to the substrate back surface Wb from the discharge nozzle 119 via the piping 313 and the gas supply pipe 117 from the freezing nitrogen gas supply unit 311 cools DIW remaining on the substrate surface Wf via the substrate W. . Thereby, a solidified body of DIW is formed inside the gap of the pattern FP formed on the substrate surface Wf (solidification step) (step S104).

  This freezing nitrogen gas is adjusted to a temperature lower than the freezing point of DIW and higher than the freezing point of the HFE liquid, for example, − (minus) 20 ° C. (degrees Celsius), so only DIW is allowed to solidify HFE. Can be solidified. In other words, a liquid solidified body can be formed inside the gap of the pattern FP on the substrate surface Wf on which the pattern FP is formed. FIG. 8 schematically shows a state in which a DIW solidified body F05 is formed inside the gap of the pattern FP while the liquid film F03 of the HFE liquid is held.

  As described above, when the HFE liquid having a freezing point lower than that of DIW is used as the first processing liquid, when DIW inside the gap of the pattern FP is solidified, the DIW temperature is higher than the freezing point of the HFE liquid. By cooling to a temperature lower than the freezing point, only DIW is solidified and the HFE liquid can maintain its fluidity while remaining in the liquid layer. Accordingly, it is possible to clean the substrate surface Wf by applying ultrasonic waves from the ultrasonic cleaning head 1715 in the ultrasonic cleaning process described later, and also hold the DIW solidified body F05 inside the gap of the pattern FP. Only the liquid film of the HFE liquid can be removed from the substrate surface Wf.

  Further, by supplying the HFE liquid at a temperature higher than the freezing point of DIW, DIW is not solidified before the DIW other than the inside of the gap of the pattern FP is excluded, and the solidified body of DIW remains particularly on the upper surface of the pattern FP. There is nothing.

  Through the first processing liquid supply step, DIW remaining on the substrate surface Wf is unevenly distributed in the gaps of the pattern FP, and DIW existing in other portions including the upper surface of the pattern FP is removed. Thereafter, a DIW solidified body is generated by the solidification step, but the portions other than the inside of the pattern FP where the DIW solidified body is generated remain covered with the liquid film of the HFE liquid. No DIW coagulum is formed on the upper surface. Further, since DIW remaining on the substrate surface Wf is covered with the HFE liquid, it does not evaporate, and remains in the gap of the pattern FP and solidifies, so that the pattern FP can be effectively reinforced.

  Further, regarding the inside of the gap of the pattern FP, when the volume of the liquid that has entered between the particles and the side wall and the bottom of the pattern FP increases (0 ° C. (degrees Celsius) water becomes 0 ° C. (degrees Celsius) ice, The volume increases by about 1.1 times), and particles and the like are separated from the substrate surface Wf by a minute distance. As a result, the adhesion force between the substrate surface Wf and the particles or the like is reduced, and further particles and the like are detached from the substrate surface Wf, and the solidified body of DIW is removed by a rinsing process described later, Particles and the like are also removed.

  After the DIW inside the gap of the pattern FP is solidified, the freezing nitrogen gas supply unit 311 stops the supply of the freezing nitrogen gas by an operation command from the control unit 93 to the solidifying means 31. Thereafter, according to an operation command from the control unit 93, the substrate rotating means 12 accelerates the substrate holding means 11 to a higher rotational speed than that at the time when the HFE liquid film F03 is formed, for example, 500 rpm, and the rotation at the rotational speed continues. Is done. FIG. 9 schematically shows a state in which the liquid film F03 of the HFE liquid formed on the substrate surface Wf is adjusted to the thickness TH. Thereby, the liquid film F03 of the HFE liquid having the thickness TH corresponding to the rotation speed can be formed on the substrate Wf. The thickness TH of the liquid film F03 of the HFE liquid can be adjusted with high accuracy by changing the rotation speed of the substrate holding means 11 (liquid film thickness control step) (step S105).

  After the adjustment of the thickness TH of the liquid film F03 of the HFE liquid is completed, the substrate rotating unit 12 decelerates the substrate holding unit 11 to, for example, 10 rpm according to an operation command from the control unit 93, and the rotation at the rotation number is continued. At the same time, the blocking member lifting mechanism 153 moves the blocking member 15 to the separated position. Thereafter, the nozzle drive mechanism 191 moves the mist supply nozzle 197 to the discharge position in accordance with an operation command from the control unit 93 to the second processing liquid supply means 22.

  After the mist supply nozzle 197 is positioned at the discharge position, the on-off valve 225 is opened by an operation command from the control unit 93 to the second processing liquid supply means 22. Thereby, DIW as the second processing liquid is pumped from the first DIW supply unit 211 to the first nozzle unit 19 through the pipe 223, and mist-like DIW is discharged from the mist supply nozzle 197 toward the substrate surface Wf. (Second treatment liquid supply step) (step S106). FIG. 10 schematically shows a state in which a DIW liquid film F07 as the second processing liquid is further formed on the HFE liquid film F03 formed on the substrate surface Wf. As a result, a DIW liquid film F07 is further formed on the HFE liquid film F03 on the substrate surface Wf, and finally a double liquid film of the HFE liquid film F03, the interface BF, and the DIW liquid film F07. A double liquid film LF having a structure is obtained.

  In this way, by adjusting the thickness TH of the HFE liquid film F03 by changing the rotation speed of the substrate W, the DIW liquid film on the HFE liquid film F03 in the ultrasonic cleaning process described later. It becomes possible to change the height of the cavitation occurring in F07 from the substrate surface Wf. Thereby, the energy of the shock wave that passes through the liquid film F03 of the HFE liquid and reaches the substrate surface Wf can be controlled.

  In addition, the laminated liquid film formation process in this embodiment is comprised by the 1st process liquid supply process and the 2nd process liquid supply process.

  Here, the HFE liquid is difficult to mix with DIW, and the HFE liquid has a higher specific gravity than DIW. Therefore, the double liquid film LF is stable, and the double liquid film LF is stably maintained even when performing ultrasonic cleaning described later.

  Further, in order to form the double liquid film LF, DIW is supplied in a mist form to the substrate surface Wf on which the HFE liquid film F03 is formed, and the DIW liquid film F07 is formed. A heavy liquid film structure can be formed stably. Furthermore, since the substrate W is rotated simultaneously with the supply of the mist-like DIW, the DIW liquid film and the interface BF can be formed flat and uniformly. As a result, the thickness TH of the liquid film F03 of the HFE liquid can be made uniform, and the in-plane uniformity of ultrasonic cleaning described later can be improved.

  After the double liquid film structure LF is formed, the on-off valve 225 is closed by the operation command from the control unit 93 to the second processing liquid supply means 22, and the nozzle drive mechanism 191 moves the mist supply nozzle 197 to the retracted position. Moving. Thereafter, according to an operation command from the control unit 93, the substrate rotating unit 12 accelerates the substrate holding unit 11 to, for example, 100 rpm, and the rotation at the rotation number is continued. Further, the head drive mechanism 173 moves the ultrasonic cleaning head 1715 to the vibration applying position in accordance with an operation command from the control unit 93 to the ultrasonic applying unit 17.

  In the state where the ultrasonic cleaning head 1715 is positioned at the vibration applying position and the vibration surface VF is in contact with the liquid film F07 of DIW, the ultrasonic oscillator 173 is pulsed by an operation command from the control unit 93 to the ultrasonic applying means 17. Start signal oscillation. Accordingly, the vibrator 1715c vibrates ultrasonically, vibrates the diaphragm 1715b, and ultrasonic vibration is applied from the vibrating surface VF to the DIW liquid film F07 (ultrasonic cleaning process) (step S107). FIG. 11 schematically shows a state where the diaphragm 1715b of the ultrasonic cleaning head 1715 is in contact with the DIW liquid film F07 and ultrasonic vibration is applied from the vibration surface VF.

  In the DIW liquid film F07, cavitation is generated and collapsed by the applied ultrasonic vibration, and a shock wave is generated accordingly. A part of this shock wave is reflected at the interface BF between the liquid film F03 of HFE liquid and the liquid film F07 of DIW. On the other hand, the shock wave that has passed through the interface BF is propagated to the substrate surface Wf through the liquid film F03 of HFE, and particles attached to the substrate surface Wf are released by the energy of the shock wave and are released into the double liquid film LF. .

  Further, when the cavitation coefficients of HFE liquid and DIW are compared, the cavitation coefficient of DIW is small. This indicates that cavitation due to ultrasonic vibration is more likely to occur in DIW than in HFE liquid. Therefore, by applying ultrasonic vibration to the double liquid film LF made of HFE liquid and DIW, cavitation occurs in the liquid film of DIW, and a shock wave necessary for ultrasonic cleaning can be formed. In this embodiment, as described above, the energy of the shock wave generated in the DIW liquid film F07 can be attenuated by the interface BF and the HFE liquid film F03 to be adjusted to an appropriate energy.

  Furthermore, since the ultrasonic wave is applied by increasing the rotation speed of the substrate W after forming the double liquid film LF, the disturbance of the interface BF is suppressed and the in-plane uniformity of ultrasonic cleaning is further increased. Is possible.

  In the first embodiment, as described above, cleaning is performed mainly using shock waves generated and collapsed as a result of cavitation. Therefore, an ultrasonic wave having a frequency at which cavitation is likely to occur in DIW, for example, 30 kHz, is applied to the DIW liquid film F07. It is given to.

  During the period from the solidification step to the ultrasonic cleaning step, at least the liquid film F03 of the HFE liquid continues to exist on the substrate surface Wf, and therefore the substrate surface Wf does not come into contact with the atmosphere. Therefore, frost does not adhere to the low-temperature substrate surface Wf, and particles and the like are not buried in the frost, so that the particles and the like attached to the substrate surface Wf can be removed well.

  Incidentally, a solid DIW solidified body F05 exists in the gap of the pattern FP, and supports the pattern FP from the side. Therefore, the influence of the vibration of the pattern FP due to the shock wave is small and the cleaning can be performed by applying a larger energy, so that a higher cleaning effect can be obtained.

  Further, while the ultrasonic wave is being applied from the ultrasonic cleaning means 17 to the DIW liquid film F07, the head drive mechanism 173 causes the ultrasonic cleaning head 1715 to be mounted on the substrate by an operation command from the control unit 93 to the ultrasonic wave applying means 17. It is preferable to swing from the vicinity of the center of W to the vicinity of the outer edge. This is because by rotating the substrate W and swinging the ultrasonic cleaning head 1715, it is possible to apply ultrasonic waves uniformly over the entire surface of the substrate surface Wf. Of course, it is also possible to apply ultrasonic waves to the substrate surface Wf by fixing the ultrasonic cleaning head 1715 at a predetermined position.

  The ultrasonic cleaning head 1715 can be swung not only once but also repeatedly. By repeating the swing, it is possible to repeatedly apply ultrasonic waves to the entire surface of the substrate surface Wf, and a higher cleaning effect can be obtained.

  After applying the ultrasonic wave for a predetermined time, the ultrasonic oscillator 173 stops the oscillation of the pulse signal and the head driving mechanism 173 retracts the ultrasonic cleaning head 1715 according to an operation command from the control unit 93 to the ultrasonic wave applying unit 17. Move to position. Thereafter, according to an operation command from the control unit 93, the blocking member lifting mechanism 153 moves the blocking member 15 to the opposite position.

  After the blocking member 15 is positioned at the facing position, the substrate rotating unit 12 accelerates the substrate holding unit 11 to, for example, 300 rpm in accordance with an operation command from the control unit 93, and the rotation at the rotation number is continued. The on-off valve 295 is opened by an operation command from the control unit 93 to the SC1 supply means 29. Thus, SC1 from the SC1 supply unit 291 is supplied from the discharge nozzle 159 to the substrate surface Wf via the pipe 293, the main pipe 20, and the second supply pipe 158. Thereby, particles and the like released from the substrate surface Wf due to application of ultrasonic vibration are removed from the substrate surface Wf together with the double liquid film LF (step S108). FIG. 12 schematically shows a state where the double liquid film LF is removed by SC1 supplied to the substrate surface Wf and the liquid film F09 of SC1 is formed on the substrate surface Wf.

  Since the zeta potential (electrokinetic potential) of the solid surface in SC1 has a relatively large value, when the space between the substrate surface Wf and the particles existing thereon is filled with SC1, the substrate surface Wf and the particles A large repulsive force acts between them. This facilitates detachment of particles and the like from the substrate surface Wf, prevents reattachment to the substrate surface Wf, and more effectively removes particles and the like from the substrate surface Wf.

  SC1 is preferably set to a temperature at which the DIW solidified body F05 existing in the gaps of the pattern FP does not melt, for example, − (minus) 0.5 ° C. (degrees Centigrade).

  When the cleaning process by SC1 is completed, the opening / closing valve 295 is closed by an operation command from the control unit 93 to the SC1 supply means 29, and the opening / closing valve 235 is opened by an operation command from the control unit 93 to the rinse liquid supply means 23. . The substrate holding means 11 continues to rotate at the same rotational speed as in the step of cleaning the substrate surface Wf with SC1 (step S108).

  Accordingly, DIW as a rinse liquid whose temperature is adjusted to, for example, 40 ° C. (degrees Celsius) from the second DIW supply unit 231 is discharged from the discharge nozzle 159 to the substrate surface Wf via the pipe 233, the main pipe 20, and the second supply pipe 158. To be supplied. As a result, the DIW coagulation F05 existing in the gaps of the pattern FP is melted and removed, and the rinsing process for washing away the SC1 remaining on the substrate surface Wf is performed (step S109). FIG. 13 schematically shows a state in which the DIW solidified body is melted and removed by the rinsing process, and the liquid film of SC1 is also removed.

  After the rinsing process, the on-off valve 235 is closed by an operation command from the control unit 93 to the rinsing liquid supply means 23. Further, in response to an operation command from the control unit 93 to the drying gas supply means 33, the drying nitrogen gas supply unit 331 starts supplying the drying nitrogen gas.

  Thus, the drying nitrogen gas from the drying nitrogen gas supply unit 331 is supplied to the substrate surface Wf via the pipe 333 and the first supply pipe 157. The nitrogen gas for drying fills the space between the blocking member 15 positioned at the opposing position and the substrate surface Wf, thereby preventing the substrate surface Wf from contacting the outside air.

  After the substrate surface Wf is blocked from the outside air, the substrate holding means 11 and the blocking member 15 are rotated at, for example, 1500 rpm in accordance with the operation command from the control unit 93 to the substrate rotating means 12 and the blocking member rotating mechanism 155. The rotation continues. Thereby, the centrifugal force is applied to the DIW, which is the rinse liquid remaining on the substrate surface Wf, to remove it, and the substrate surface Wf is dried (step S110).

  After the drying of the substrate W is completed, the drying nitrogen gas supply unit 331 stops the supply of the drying nitrogen gas according to an operation command from the control unit 93 to the drying gas supply means 33. Further, the substrate rotating means 12 stops the rotation of the substrate holding means 11 according to an operation command from the control unit 93, and the blocking member rotating mechanism 155 stops the rotation of the blocking member 15. After the rotation of the substrate holding means 11 is stopped, the substrate rotating means 12 positions the substrate holding means 11 at a position suitable for delivery of the substrate W according to an operation command from the control unit 93. Further, the blocking member lifting mechanism 153 moves the blocking member 15 to the retracted position in accordance with an operation command from the control unit 93.

  After the substrate holding unit 11 is positioned at a position suitable for delivery of the substrate W, the chuck pin driving mechanism 116 opens the chuck pin 115 according to an operation command from the control unit 93 to the substrate holding unit 11.

  Thereafter, according to an operation command from the control unit 93, the substrate transport device 51 takes out the processed substrate W in the processing unit 1 and carries it into a predetermined position of the cassette 8 placed on the placement unit 71 (step S111). ), A series of processing ends.

  As described above, in the first embodiment, with respect to the substrate surface Wf on which the pattern FP is formed, liquid is removed from the substrate surface Wf excluding the inside of the gap of the pattern FP by the laminated liquid film forming unit, and the substrate surface Wf is processed. A liquid film composed of the first processing liquid and the second processing liquid is formed as the liquid. Thereby, the liquid can be isolated and remained only in the gaps of the pattern FP, and a solidified liquid body is not formed on the upper surface of the pattern FP in the subsequent solidification process. Further, the liquid film of the treatment liquid is maintained even after the liquid solidified body is formed, and ultrasonic waves are applied to the liquid film of the treatment liquid. For this reason, the substrate surface Wf is shielded from the atmosphere by the liquid film of the processing liquid, and frost does not adhere to the substrate surface Wf. For this reason, it becomes possible to satisfactorily clean the upper surface of the pattern FP and the substrate surface Wf on which the pattern FP is not formed.

  Further, since the liquid and the first processing liquid are difficult to mix with each other, even if the liquid on the upper surface of the substrate surface Wf is excluded, the first processing liquid does not enter the gap of the pattern FP, and the liquid inside the gap of the pattern FP. There is no exclusion. Moreover, the first treatment liquid does not cause a change in the freezing point of the liquid when mixed with the liquid.

  Further, the DIW solidified body F05 exists in the gap of the pattern FP, and the pattern FP is supported from the side wall, so that the influence of ultrasonic cleaning is small. Therefore, the thickness TH of the liquid film F03 of the HFE liquid can be reduced to increase the energy propagated to the substrate surface Wf, and a higher cleaning effect can be obtained.

  In the first embodiment, cooling is performed by discharging freezing nitrogen gas to the back surface Wb of the substrate W in the freezing step. However, other gaseous refrigerant such as dry air or liquid refrigerant such as hydrofluorocarbon is used as the substrate. It is also possible to cool by other well-known methods, such as discharging to the back surface Wb of W, or making a cooling plate contact or adjoin to the substrate back surface Wb.

<Second embodiment>
Next, a second embodiment of the substrate processing apparatus according to the present invention will be described. FIG. 14 is a schematic diagram showing the configuration of the processing unit 1 in the second embodiment. FIG. 15 is a flowchart showing the operation of the processing unit 1 of FIG. FIG. 16 is a schematic diagram for explaining the operation of the processing unit 1 of FIG.

  The second embodiment is greatly different from the first embodiment in that ultrasonic cleaning is performed without forming the double liquid film LF. That is, the post-processing liquid supply means 22 for supplying DIW on the liquid film of the HFE liquid provided in the first embodiment is not provided, but the ultrasonic cleaning means 17 directly applies the HFE liquid held on the substrate surface Wf. The point is that ultrasonic cleaning is performed by applying sound waves.

  Another difference is that in order to solidify DIW, an HFE liquid having a temperature lower than that of DIW is supplied to the substrate surface Wf. That is, instead of the freezing means 31 provided in the first embodiment, a post-treatment liquid supply means 27 for supplying an HFE liquid having a temperature lower than the freezing point of DIW is provided.

  Since other configurations are basically the same as those of the substrate processing apparatus 91 and the processing unit 1 shown in FIGS. 1 to 13, the following description will be made on the different points, and the same reference numerals will be given to the different points. Therefore, description of the configuration is omitted.

  Further, the pretreatment HFE liquid supply unit 251 in the second embodiment is the same as the HFE supply unit 251 in the first embodiment, and is distinguished from the posttreatment HFE supply unit 271 of the posttreatment liquid supply unit 27 described later. Therefore, only the name is changed.

  The post-processing liquid supply means 27 includes a post-processing HFE liquid supply unit 271, an on-off valve 275, a pipe 273, a main pipe 20, a second supply pipe 158, and a discharge nozzle 159.

  When the on-off valve 275 is opened by an operation command from the control unit 93, post-processing HFE liquid as post-processing liquid is supplied from the post-processing HFE liquid supply unit 271 through the pipe 273, the main pipe 20, and the second supply pipe 158. It is supplied from the discharge nozzle 159 to the substrate surface Wf.

  The coagulation means in the second embodiment is constituted by post-treatment liquid supply means 27. Moreover, the coagulation process in the second embodiment includes a post-treatment liquid supply process.

  The laminated liquid film forming means in the second embodiment is constituted by a pretreatment liquid supply means 25. Further, the laminated liquid film forming means in the second embodiment is constituted by a pretreatment liquid supply step.

  In the second embodiment, similarly to the first embodiment, the substrate W is carried in (step S201), the DIW is supplied (step S202), and the DIW remaining on the substrate surface Wf by the pretreatment HFE liquid is removed (step S203). Is done. In the second embodiment, the on-off valve 275 is closed by an operation command from the control unit 93 in preparation for loading the substrate W.

  After the liquid film F03 of HFE liquid for pretreatment as a pretreatment liquid is formed on the entire substrate surface Wf on the upper layer of the pattern FP, DIW other than the inside of the gap of the pattern FP on the substrate surface Wf is removed, and then the control unit 93 The on-off valve 255 is closed by an operation command from the first to the pretreatment liquid supply means 25, and the supply of the pretreatment HFE liquid as the pretreatment liquid to the substrate surface Wf is stopped.

  Thereafter, the on-off valve 275 is opened by an operation command from the control unit 93 to the post-processing liquid supply means 27, and the post-processing HFE liquid as the post-processing liquid from the post-processing HFE liquid supply unit 271 is connected to the pipe 273. It is supplied from the discharge nozzle 159 to the substrate surface Wf via the pipe 20 and the second supply pipe 158. Here, the post-processing HFE liquid freezes the DIW existing in the gaps of the pattern FP, so that the temperature is lower than the freezing point of the DIW and higher than the freezing point of the HFE liquid, for example, − (minus) 10 ° C. (Celsius). Adjusted. The substrate holding means 11 continues to rotate at the same rotational speed as in the step of supplying the pretreatment HFE liquid (step S203).

  The post-processing HFE liquid supplied to the substrate surface Wf spreads over the entire substrate surface Wf while removing the pre-processing HFE liquid, and forms a liquid film of the post-processing HFE liquid. At this time, the cold heat of the post-processing HFE liquid is conducted to DIW existing in the gaps of the pattern FP, and a DIW solidified body F05 is formed (solidification step) (step S204). FIG. 16 schematically shows a state in which the post-processing HFE liquid is supplied to the substrate surface Wf to form the liquid film F04 of the post-processing HFE liquid, and the DIW inside the gap of the pattern FP is solidified.

  After the DIW solidified body F05 is formed, the on-off valve 275 is closed by an operation command from the control unit 93 to the post-treatment liquid supply means 27. Further, the blocking member lifting mechanism 153 moves the blocking member 15 to the retracted position in accordance with an operation command from the control unit 93. Since the post-processing HFE liquid is intended to form a DIW solidified body F05, the post-processing HFE liquid must be supplied to the substrate surface Wf before the DIW solidified body F05 is formed. It is also possible to solidify DIW by cooling and cooling the liquid film F04 of the post-processing HFE liquid remaining on the substrate surface Wf.

  Through the laminated liquid film forming step, DIW remaining on the substrate surface Wf is unevenly distributed in the gaps of the pattern FP, and DIW existing in other portions including the upper surface of the pattern FP is removed. Thereafter, a DIW solidified body is generated by the solidification step, but the portions other than the inside of the pattern FP where the DIW solidified body is generated remain covered with the liquid film of the HFE liquid. No DIW coagulum is formed on the upper surface. Further, since DIW remaining on the substrate surface Wf is covered with the HFE liquid, it does not evaporate, and remains in the gap of the pattern FP and solidifies, so that the pattern FP can be effectively reinforced.

  In addition, regarding the inside of the gap of the pattern FP, when the volume of the liquid that has entered between the particles and the side wall and the bottom of the pattern FP increases (when water at 0 ° C. (celsius) becomes ice at 0 ° C. (celsius), The volume increases approximately 1.1 times), and particles and the like are separated from the substrate surface Wf by a minute distance. As a result, the adhesion force between the substrate surface Wf and the particles or the like is reduced, and further particles and the like are detached from the substrate surface Wf, and the solidified body of DIW is removed by a rinsing process described later, Particles and the like are also removed.

  After the supply of the second HFE liquid is stopped, the substrate rotating unit 12 accelerates the rotation speed of the substrate holding unit 11 to, for example, 100 rpm according to an operation command from the control unit 93, and the rotation at the rotation number is continued. Further, the head drive mechanism 173 moves the ultrasonic cleaning head 1715 to the vibration applying position in accordance with an operation command from the control unit 93 to the ultrasonic applying unit 17.

  In the state where the ultrasonic cleaning head 1715 is positioned at the vibration applying position and the vibration surface VF is in contact with the liquid film F04 of the second HFE liquid, the ultrasonic oscillator 173 is operated by an operation command from the control unit 93 to the ultrasonic wave applying means 17. Starts oscillation of the pulse signal. As a result, the vibrator 1715c vibrates ultrasonically, vibrates the diaphragm 1715b, and ultrasonic vibration is applied from the vibrating surface VF to the liquid film of the second HFE liquid (ultrasonic cleaning process) (step S205).

  During the period from the freezing step to the ultrasonic cleaning step, since the liquid film of the HFE liquid continues to exist on the substrate surface Wf, the substrate surface Wf does not come into contact with the atmosphere. Therefore, frost does not adhere to the low-temperature substrate surface Wf, and particles and the like are not buried in the frost, so that the particles and the like attached to the substrate surface Wf can be removed well.

  Incidentally, a solid DIW solidified body F05 exists in the gap of the pattern FP, and supports the pattern FP from the side. Therefore, since the influence on the pattern FP by the ultrasonic vibration is small and cleaning can be performed by applying a larger energy, a higher cleaning effect can be obtained.

  Moreover, in 2nd embodiment, it does not have the double liquid film structure LF like 1st embodiment, and there is no reflection by the interface BF between two liquid films. Therefore, it becomes possible to propagate more ultrasonic vibration energy from the ultrasonic cleaning head 1715 to the substrate surface Wf, and higher cleaning ability can be obtained.

  While the ultrasonic wave is being applied from the ultrasonic cleaning means 17 to the liquid film F04 of the second HFE liquid, the head drive mechanism 173 causes the ultrasonic cleaning head to operate in response to an operation command from the control unit 93 to the ultrasonic wave applying means 17. It is preferable to swing 1715 from the vicinity of the center of the substrate W to the vicinity of the outer edge. This is because by rotating the substrate W and swinging the ultrasonic cleaning head 1715, it is possible to apply ultrasonic waves uniformly over the entire surface of the substrate surface Wf. Of course, it is also possible to apply ultrasonic waves to the substrate surface Wf by fixing the ultrasonic cleaning head 1715 at a predetermined position.

  The ultrasonic cleaning head 1715 can be swung not only once but also repeatedly. By repeating the swing, it is possible to repeatedly apply ultrasonic waves to the entire surface of the substrate surface Wf, and a higher cleaning effect can be obtained.

  Here, since the HFE liquid has a large cavitation coefficient as described above, cavitation hardly occurs. Therefore, in the second embodiment, the frequency of the pulse signal oscillated from the ultrasonic oscillator 173 is set to 1 MHz, for example, and the vibration acceleration of the ultrasonic vibration is transmitted to the substrate surface Wf through the HFE liquid and attached to the substrate surface Wf. Cleaning is performed by removing particles and the like.

  After applying the ultrasonic wave for a predetermined time, the ultrasonic oscillator 173 stops the oscillation of the pulse signal according to the operation command from the control unit 93 to the ultrasonic wave applying means 17 and the head driving mechanism 173 moves to the retracted position.

  Thereafter, in response to an operation command from the control unit 93, the blocking member lifting mechanism 153 moves the blocking member 15 to the opposite position, and cleaning with SC1 (step S206) and rinsing with DIW (step S207) as in the first embodiment. Then, drying of the substrate W by high-speed spin (step S208) and unloading of the processed substrate W (step S209) are performed, and a series of processing is completed.

  In the second embodiment, although the post-treatment HFE liquid at a temperature lower than the freezing point of DIW is supplied to the substrate surface Wf as the freezing step, it can also be cooled from the substrate back surface Wb. is there. In this case, since cooling is performed from both the front and back of the substrate W, the time required for freezing the DIW is shortened.

  Further, without supplying the post-processing HFE liquid, the DIW solidified body is cooled by cooling from the substrate back surface Wb in the same manner as in the first embodiment while the liquid film of the pre-processing HFE liquid is held on the substrate surface Wf. It is also possible to perform cleaning by applying ultrasonic waves from the ultrasonic cleaning head 1715 to the pretreatment HFE liquid that is generated and held on the substrate surface Wf.

  In the second embodiment, the HFE liquid is used as the pretreatment liquid and the posttreatment liquid, which are treatment liquids. However, the liquid is difficult to mix with the liquid and has a freezing point lower than the freezing point of the liquid. It is possible to use other liquids. For example, o-xylene (1,2-dimethylbenzene) (freezing point:-(minus) 25.2 ° C (Celsius)), m-xylene (1,3-dimethylbenzene) (freezing point:-(minus) 48.9 ° C (Celsius)), trichloromethane (freezing point:-(minus) 63.5 ° C (Celsius)), tetrachloroethylene (freezing point:-(minus) 22.2 ° C (Celsius)), and the like. In addition, these process liquids may be diluted.

  In the second embodiment, the same HFE liquid is supplied by changing the temperature only as the pretreatment liquid and the posttreatment liquid, but it is difficult to mix with the liquid and has a freezing point lower than the freezing point of the liquid. If so, the pretreatment liquid and the posttreatment liquid can be supplied as different liquids. In particular, when the pretreatment liquid and the posttreatment liquid are difficult to mix with each other, heat transfer due to mixing with each other in the interface area between the two treatment liquids is reduced, and it is necessary to perform freezing by shaking to the area where both treatment liquids are mixed. This is preferable because the supply amount of the processing liquid can be reduced.

<Third embodiment>
Next, a third embodiment of the substrate processing apparatus according to the present invention will be described. FIG. 17 is a front sectional view showing the configuration of the ultrasonic cleaning nozzle used in the processing unit of the third embodiment, and FIG. 18 is a flowchart showing the operation of the processing unit 1 of the third embodiment.

  The third embodiment differs greatly from the first embodiment in that ultrasonic cleaning is performed without forming the double liquid film LF, and in place of the ultrasonic cleaning unit 171 in the first embodiment. A second nozzle portion 35 having a cleaning nozzle is provided, and ultrasonic cleaning is performed by supplying the SC1 with ultrasonic waves to the substrate surface Wf. Therefore, in 3rd embodiment, the 2nd process liquid supply means 22 in 1st embodiment is not provided.

  Since other configurations are basically the same as those of the substrate processing apparatus 91 and the processing unit 1 shown in FIGS. 1 to 13, the following description will be made on the different points, and the same reference numerals will be given to the different points. Therefore, description of the configuration is omitted.

  The second nozzle part 35 has the same mechanism as the first nozzle part 19 in the first embodiment. An ultrasonic cleaning nozzle 357 is attached to the tip of the arm 35 of the second nozzle portion 35. The SC1 supply unit is not discharged from the center of the blocking member 15 through the second supply pipe 158 as in the first embodiment, but is connected to the ultrasonic cleaning nozzle 357 via the pipe 293.

  That is, a nozzle driving mechanism 351 is provided on the outer side in the circumferential direction of the processing cup 13 as a driving source for scanning the second nozzle portion 35. A rotation shaft 353 is connected to the nozzle drive mechanism 351, and an arm 355 is connected to the rotation shaft 353 so as to extend in the horizontal direction. An ultrasonic cleaning nozzle 357 is attached to the tip of the arm 355. . When the nozzle drive mechanism 351 is driven by an operation command from the control unit 93, the arm 355 is a position where the discharge position above the substrate surface Wf around the rotation shaft 353 and the outer side in the circumferential direction of the processing cup 13. It swings between the retracted positions.

  The second nozzle part 35 is connected to the SC1 supply part 291 via a pipe 293, and an opening / closing valve 295 is inserted in the pipe 293. The on-off valve 295 is normally closed, and the on-off valve 295 is opened by an operation command from the control unit 93 when SC1 as the cleaning liquid is supplied to the substrate surface Wf as described later. As a result, SC1 is supplied from the SC1 supply unit 291 to the second nozzle unit 35 via the pipe 293, and discharged from the ultrasonic cleaning nozzle 357 toward the substrate surface Wf.

  FIG. 17 is a front sectional view of the ultrasonic cleaning nozzle 357. The ultrasonic cleaning nozzle is formed on the upper wall surface of the body portion 3571 having a cylindrical shape in the upper half portion and a conical shape in the lower half portion and having a circular discharge port 3573 on the lower end surface. A vibration plate 3577 fixed at the position of the through hole 3575 and an ultrasonic transducer 3579 fixed on the vibration plate 3577 are provided. Further, a through hole 3581 formed in the upper side wall surface of the body portion 3571 is connected to the SC1 supply portion 291 through a pipe 293. The body portion 3571 is formed of a material having chemical resistance such as a fluororesin.

  The ultrasonic vibrator 3579 is electrically connected to the ultrasonic oscillator 173 via the cable 175, and when a pulse signal is output from the ultrasonic oscillator 173 to the ultrasonic vibrator 3579, the ultrasonic vibrator 3579 is supersonic. Ultrasonic vibration is applied to SC1 that vibrates with sound waves and fills the inside of the body portion 3571 through the vibration plate 3577.

  The ultrasonic cleaning means 34 in the third embodiment includes a second nozzle part 35, a cable 316, an ultrasonic oscillator 173, and a cleaning liquid supply part 29.

  The cleaning liquid supply unit 29 includes a pipe 293, an on-off valve 295, and an SC1 supply unit 291.

  In the third embodiment, similarly to the first embodiment, the substrate W is carried in (step S301), DIW is supplied (step S302), DIW remaining on the substrate surface Wf by the HFE liquid (step S303), and the back surface of the substrate. A freezing process (step S304) is performed in which a refrigerant is supplied to Wb to form a DIW solidified body F05.

  After the DIW solidified body F05 is formed, the freezing nitrogen gas supply unit 311 stops the supply of the freezing nitrogen gas in response to an operation command from the control unit 93 to the solidifying means 31. Thereafter, according to an operation command from the control unit 93, the substrate rotating unit 12 changes the rotation speed of the substrate holding unit 11 to, for example, 100 rpm, and the rotation at the rotation number is continued. 15 is moved to the separation position. Thereafter, the nozzle drive mechanism 351 moves the ultrasonic cleaning nozzle 357 to the discharge position in accordance with an operation command from the control unit 93 to the ultrasonic cleaning means 34.

  After the ultrasonic cleaning nozzle 357 is positioned at the discharge position, the on-off valve 295 is opened by an operation command from the control unit 93 to the ultrasonic cleaning means 34, and the ultrasonic oscillator 173 starts oscillation of a pulse signal. As a result, the vibrator 3579 is ultrasonically vibrated, and ultrasonic vibration is applied to the SC 1 filled inside the body portion 3571 via the vibration plate 3577 and is ejected from the ejection port 3573 onto the substrate surface Wf (ultrasonic cleaning process). (Step S305).

  The SC1 to which ultrasonic vibration is applied by the ultrasonic cleaning nozzle 357 and discharged onto the substrate surface Wf separates particles and the like attached to the substrate surface Wf from the ultrasonic vibration and separates the substrate surface Wf from the substrate surface Wf. The substrate surface Wf is cleaned by removing the existing HFE liquid.

  The liquid film of the HFE liquid continues to exist on the substrate surface Wf after the freezing process until the ultrasonic cleaning process. In the ultrasonic cleaning process, although SC1 is replaced with the HFE liquid, a liquid film is still formed on the substrate surface Wf. For this reason, the substrate surface Wf does not come into contact with the atmosphere, and frost does not adhere to the low-temperature substrate surface Wf, so that particles or the like are not buried in the frost. Therefore, it is possible to satisfactorily remove particles and the like attached to the substrate surface Wf.

  Incidentally, a solid DIW solidified body F05 exists in the gap of the pattern FP, and supports the pattern FP from the side. Therefore, the influence of the vibration of the pattern FP due to the shock wave is small and the cleaning can be performed by applying a larger energy, so that a higher cleaning effect can be obtained.

  Moreover, in 3rd embodiment, it does not have the double liquid film structure LF like 1st embodiment, and there is no reflection by the interface BF between two liquid films. Therefore, since it is possible to apply more energy of ultrasonic vibration propagated by SC1, which is the cleaning liquid discharged from the ultrasonic cleaning nozzle 357, to the substrate surface Wf, higher cleaning ability can be obtained.

  In addition, the ultrasonic cleaning is performed while discharging SC1 from the ultrasonic cleaning nozzle 357, and the liquid film of HFE is excluded in parallel with the cleaning of the substrate surface Wf. Can be shortened.

  While the SC1 with ultrasonic waves applied to the substrate surface Wf is discharged from the ultrasonic cleaning nozzle 357, the ultrasonic cleaning means 34 performs ultrasonic cleaning according to an operation command from the control unit 93 to the ultrasonic cleaning means 34. The nozzle 357 is preferably swung from the vicinity of the center of the substrate W to the vicinity of the outer edge. This is because the ultrasonic wave can be applied uniformly over the entire surface Wf of the substrate by rotating the substrate W and swinging the ultrasonic cleaning nozzle 357. Of course, it is also possible to apply ultrasonic waves to the substrate surface Wf by fixing the position of the ultrasonic cleaning nozzle 357 so that a predetermined position, for example, the discharged SC1 hits the vicinity of the center of the substrate W.

  The oscillation of the ultrasonic cleaning nozzle 357 can be repeated not only once. By repeating the swing, it is possible to repeatedly apply ultrasonic waves to the entire surface of the substrate surface Wf, and a higher cleaning effect can be obtained.

  Since the zeta potential (electrokinetic potential) of the solid surface in SC1 has a relatively large value, when the space between the substrate surface Wf and the particles existing thereon is filled with SC1, the substrate surface Wf and the particles A large repulsive force acts between them. Thereby, the effect of removing particles and the like by ultrasonic vibration is promoted, and the reattachment of particles and the like to the substrate surface Wf can be prevented, and the particles and the like can be effectively removed from the substrate surface Wf.

  Further, SC1 is preferably set to a temperature at which the DIW solidified body F05 existing in the gap of the pattern FP is not melted, for example, − (minus) 0.5 ° C. (Celsius).

In the third embodiment, SC1 is used as a liquid for ultrasonic cleaning by being discharged from the ultrasonic cleaning nozzle 357 to the substrate surface Wf. However, the liquid that can be used for ultrasonic cleaning is not limited to this, but DIW or ozone. Water, SC2 (Standard Clean 2: a mixed aqueous solution of hydrochloric acid (chemical formula: HCl) and hydrogen peroxide (chemical formula: H ₂ O ₂ )) and other chemicals can also be used.

  After the ultrasonic cleaning of the substrate surface Wf is completed, the on-off valve 295 is closed by an operation command from the control unit 93 to the ultrasonic cleaning means 34, and the ultrasonic oscillator 173 stops the oscillation of the pulse signal. Further, the nozzle drive mechanism 351 moves the ultrasonic cleaning nozzle 357 to the retracted position in accordance with an operation command from the control unit 93 to the ultrasonic cleaning means 34.

  Thereafter, in response to an operation command from the control unit 93, the blocking member lifting mechanism 153 moves the blocking member 15 to the opposite position, and rinse processing by DIW (step S306) and the substrate surface Wf by high-speed spin as in the first embodiment. Drying (step S307) and unloading of the processed substrate W (step S308) are performed, and a series of processing ends.

  In the third embodiment, the HFE liquid is used as the processing liquid, but other liquids are used as long as they are difficult to mix with the liquid and have a freezing point lower than the freezing point of the liquid. It is also possible. For example, o-xylene (1,2-dimethylbenzene) (freezing point:-(minus) 25.2 ° C (Celsius)), m-xylene (1,3-dimethylbenzene) (freezing point:-(minus) 48.9 ° C (Celsius)), trichloromethane (freezing point:-(minus) 63.5 ° C (Celsius)), tetrachloroethylene (freezing point:-(minus) 22.2 ° C (Celsius)), and the like. In addition, these process liquids may be diluted.

<Others>
The present invention is not limited to the above-described embodiment, and various modifications other than those described above can be made without departing from the spirit of the present invention. For example, in each of the above embodiments, DIW is supplied to the substrate surface Wf as a freezing liquid, but the freezing liquid is not limited to DIW, and pure water, ultrapure water, hydrogen water, Even a liquid such as carbonated water or SC1 can be used.

DESCRIPTION OF SYMBOLS 1 Processing unit 11 Substrate holding means 12 Substrate rotating means 13 Processing cup 15 Blocking member 17 Ultrasonic cleaning means 21 Liquid supply means 22 Second processing liquid supply means 23 Rinse liquid supply means 25 First processing liquid supply means (FIG. 3), Pretreatment liquid supply means (FIG. 14)
27 Post-treatment liquid supply means 29 SC1 supply means 31 Coagulation means 33 Drying gas supply means 91 Substrate processing apparatus 93 Control unit

Claims (9)

A solidification step of forming a liquid solidified body in the gap between the patterns of the substrate on which the predetermined pattern is formed, and holding a liquid film on the surface of the substrate;
An ultrasonic cleaning step of cleaning the substrate surface by applying ultrasonic vibration to the substrate through the liquid film held on the substrate surface while maintaining the state where the solidified body is formed inside the gap of the pattern And a substrate processing method. The substrate processing method according to claim 1,
The liquid film is
A substrate processing method comprising a processing liquid which is difficult to mix with the liquid and has a freezing point lower than the freezing point of the liquid. The substrate processing method according to claim 2,
Prior to the solidification process,
The processing liquid for forming the liquid film is supplied to the surface of the substrate on which the pattern is formed and the liquid adheres, and the liquid is removed from the substrate surface while the liquid remains in the gap of the pattern. And a laminated liquid film forming step of forming a liquid film of the processing liquid on the upper layer of the liquid inside the pattern gap. The substrate processing method according to claim 3,
The treatment liquid is
A substrate processing method comprising at least a first processing liquid having a temperature higher than a freezing point of the liquid. The substrate processing method according to claim 4,
The laminated liquid film forming step includes
A substrate processing method comprising a first processing liquid supply step for supplying the first processing liquid. The substrate processing method according to claim 5,
The laminated liquid film forming step further includes a step of rotating the substrate, and the first processing liquid is supplied near the center of the substrate. The substrate processing method according to claim 6, comprising:
The first treatment liquid supply step includes
A substrate processing method for supplying a first processing liquid having a temperature near a freezing point of the liquid. A substrate processing method according to any one of claims 1 to 7,
A substrate processing method further comprising a liquid supply step of supplying the liquid to the substrate surface. Substrate holding means for holding a substrate on which a predetermined pattern is formed and liquid is attached;
Substrate rotating means for rotating the substrate;
A processing liquid is supplied toward the surface of the substrate held by the substrate holding means, and the liquid is removed from the substrate surface while the liquid remains in the pattern gap, and the liquid inside the pattern gap is removed. A laminated liquid film forming means for forming a liquid film of the treatment liquid on an upper layer of the liquid;
A coagulation means for holding a liquid film of the processing liquid and coagulating the liquid remaining in the gap of the pattern to form a solidified body in the gap of the pattern;
Ultrasonic cleaning means for cleaning the substrate surface by applying ultrasonic vibration to the substrate through a liquid film formed on the substrate surface while maintaining the state where the solidified body is formed inside the gap of the pattern; A substrate processing apparatus comprising:

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