JP2017224783A - Substrate processing apparatus and substrate processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a substrate processing apparatus capable of removing liquid adhering to the surface of a substrate efficiently, while preventing a pattern formed on the surface of the substrate from collapsing.SOLUTION: A drying auxiliary liquid 61 containing a drying auxiliary material is supplied to a surface Wf of a substrate W to which IPA60 is adhered, the drying auxiliary liquid 61 is solidified on the surface Wf of the substrate W by precipitation or freezing, thus forming a coagulation film 62 of the drying auxiliary material. Thereafter, a part of the drying auxiliary material of the coagulation film 62 is removed by solid body removing means 52, in the solid state by suction or the like, thus thinning the coagulation film 62. Thereafter, the coagulation film 62 is changed from solid state to gas state by sublimation or the like, without going through the liquid state, and removed from the surface Wf of the substrate W, thus drying the substrate W. Sublimation or the like can be performed efficiently by thinning the coagulation film 62.SELECTED DRAWING: Figure 7

Description

  The present invention includes a semiconductor substrate, a glass substrate for photomask, a glass substrate for liquid crystal display, a glass substrate for plasma display, a substrate for FED (Field Emission Display), a substrate for optical disk, a substrate for magnetic disk, a substrate for magneto-optical disk, etc. The present invention relates to a substrate processing apparatus for removing liquid adhering to various substrates (hereinafter simply referred to as “substrate”) from the substrate.

  In the manufacturing process of electronic components such as semiconductor devices and liquid crystal display devices, after various wet processes using liquid are performed on the substrate, the substrate is subjected to a drying process to remove the liquid attached to the substrate by the wet process. Apply to.

  Examples of the wet process include a cleaning process for removing contaminants on the substrate surface. For example, reaction by-products (etching residues) are present on the substrate surface on which a fine pattern having irregularities is formed by a dry etching process. Further, in addition to the etching residue, there is a possibility that metal impurities, organic contaminants, and the like are attached to the substrate surface, and in order to remove these substances, a cleaning process such as supplying a cleaning liquid to the substrate is performed.

  After the cleaning process, a rinsing process for removing the cleaning liquid with a rinsing liquid and a drying process for drying the rinsing liquid are performed. The rinsing process includes a rinsing process in which a rinsing liquid such as deionized water (DIW) is supplied to the substrate surface to which the cleaning liquid adheres to remove the cleaning liquid on the substrate surface. Then, the drying process which dries a board | substrate by removing a rinse liquid is performed.

  In recent years, with the miniaturization of a pattern formed on a substrate, the aspect ratio (ratio of height to width in a pattern convex portion) at a convex portion of a pattern having irregularities has increased. For this reason, during the drying process, the surface tension acting on the boundary surface between the liquid such as the cleaning liquid or the rinse liquid that has entered the concave portion of the pattern and the gas in contact with the liquid attracts the adjacent convex portion in the pattern, and the pattern There was a problem of collapse.

  As a technique for preventing the collapse of the pattern due to such surface tension, Patent Document 1 and Patent Document 2 supply a solution of a sublimable substance on a substrate and dry the solvent in the solution. A drying technique for filling a substrate with a solid phase sublimable substance and sublimating the sublimable substance is shown. Since the surface tension does not act on the interface between the solid and the gas in contact with the solid, the collapse of the pattern due to the surface tension can be suppressed.

  Patent Document 3 discloses a drying technique in which a melt of tertiary butanol is supplied to a substrate to which a liquid is attached, and the solid butanol is solidified on the substrate to form a solidified body, and then the tertiary butanol is sublimated and removed. It is shown.

  In Patent Document 4, a naphthalene solution is supplied onto a substrate and naphthalene is deposited on the surface of the substrate to form a naphthalene film. Then, IPA (isopropyl alcohol) is supplied to dissolve the upper portion of the naphthalene film. A technique for reducing the film thickness is disclosed. Thereby, the processing time concerning the sublimation of naphthalene can be reduced.

JP 2012-243869 A JP 2013-258272 A JP, 2015-142069, A Japanese Patent Laying-Open No. 2015-50414

  In the technique of Patent Document 4, the processing time required for sublimation of naphthalene is reduced by supplying a solution for dissolving naphthalene deposited on the substrate surface. However, in such a configuration, the supplied IPA penetrates from the upper part of the naphthalene film to the inside and reaches the substrate surface, so that the pattern may be collapsed. The risk of pattern collapse becomes more prominent as the naphthalene film is made thinner, and this has been a problem in making the film thinner while preventing pattern collapse.

  Further, in the technique of Patent Document 4, since a mixed solution in which naphthalene is dissolved in IPA is generated as a drainage liquid, it is difficult to separate IPA and naphthalene after the drainage recovery, and there is a problem that the waste liquid treatment cost increases. .

  The present invention has been made in view of the above problems, and a substrate processing apparatus capable of more efficiently removing the liquid adhering to the surface of the substrate while preventing the pattern formed on the surface of the substrate from collapsing. An object is to provide a substrate processing method.

  In order to solve the above-mentioned problems, a substrate processing apparatus according to the first invention of the present application includes a drying auxiliary liquid supply means for supplying a drying auxiliary liquid containing a drying auxiliary substance to the surface of a substrate to which the processing liquid is attached; Solidification means for changing the drying auxiliary substance contained in the auxiliary liquid into a solid state by precipitation or solidification on the surface of the substrate, and the drying auxiliary substance in the solid state on the surface of the substrate maintain the solid state. A solid removal means for removing from the surface of the substrate, and a gasification means for changing the solid dry auxiliary substance on the surface of the substrate into a gaseous state by sublimation, thermal decomposition or oxidation, and removing from the substrate. Is provided.

  A second invention of the present application is the substrate processing apparatus of the first invention, wherein the solid removing means sprays a fluid onto the surface of the substrate to remove the drying auxiliary substance in the solid state from the surface of the substrate. It is characterized by doing.

  A third invention of the present application is the substrate processing apparatus of the second invention, wherein the solid removing means sprays a gas having a temperature lower than the melting point of the drying auxiliary substance onto the surface of the substrate.

  A fourth invention of the present application is the substrate processing apparatus according to the first invention, wherein the solid removal means is a suction means for sucking the drying auxiliary substance in a solid state on the surface of the substrate.

  A fifth invention of the present application is the substrate processing apparatus according to the first invention, wherein the solid removing means is a scraping means for scraping off the solid dry auxiliary substance on the surface of the substrate.

  A sixth invention of the present application is the substrate processing apparatus according to any one of the first to fifth inventions, wherein the drying auxiliary liquid supply means supplies the dried auxiliary liquid containing the molten drying auxiliary substance to the substrate. Supplying to the surface, the solidification means solidifies the melted drying auxiliary substance on the surface of the substrate.

  A seventh invention of the present application is the substrate processing apparatus according to any one of the first to fifth inventions, wherein the drying auxiliary liquid supply means includes the solution of the drying auxiliary substance dissolved in a solvent. Is supplied to the surface of the substrate, and the solidification means removes the solvent contained in the drying auxiliary liquid and deposits the drying auxiliary material on the surface of the substrate.

  An eighth invention of the present application is the substrate processing apparatus according to any one of the first to seventh inventions, wherein the gasifying means sublimates the drying auxiliary substance in a solid state on the surface of the substrate to thereby form the substrate. It is characterized by removing from.

  A ninth invention of the present application is the substrate processing apparatus of the eighth invention, wherein the drying auxiliary substance is pure water, tertiary butanol, or 1,1,2,2,3,3,4-heptafluorocyclopentane. It is characterized by being.

  In order to solve the above problems, a substrate processing method according to the tenth invention of the present application includes a drying auxiliary liquid supplying step of supplying a drying auxiliary liquid containing a drying auxiliary substance to the surface of the substrate to which the processing liquid is attached, and the drying The solidification step of changing the drying auxiliary substance contained in the auxiliary liquid into a solid state by precipitation or solidification on the surface of the substrate, and the solid state of the drying auxiliary substance in the solid state on the surface of the substrate are maintained in a solid state. The solid removal step of removing from the surface of the substrate, and after the solid removal step, the drying auxiliary substance in the solid state on the surface of the substrate is sublimated, pyrolyzed or oxidized to change to a gaseous state, And a gasification step for removing from the substrate.

  In the present invention, the drying auxiliary substance in the solid state on the surface of the substrate is removed from the surface of the substrate while maintaining the solid state, thereby preventing collapse of the pattern formed on the surface of the substrate. The liquid adhering to the surface of can be removed more efficiently.

It is a figure which shows the schematic side view of the substrate processing apparatus which concerns on 1st Embodiment. It is a figure which shows the schematic plan view of the substrate processing apparatus which concerns on 1st Embodiment. It is a figure which shows schematic structure of the control unit which concerns on 1st Embodiment. It is a figure which shows schematic structure of a drying auxiliary liquid tank. It is a figure which shows schematic structure of a gas tank. It is a flowchart which shows operation | movement of a substrate processing apparatus. It is a figure which shows the mode of the board | substrate in each process of the substrate processing which concerns on 1st Embodiment. It is a figure which shows the schematic side view of the substrate processing apparatus which concerns on 4th Embodiment. It is a figure which shows the schematic side view of the substrate processing apparatus which concerns on 5th Embodiment. It is a figure which shows the schematic plan view of the substrate processing apparatus which concerns on 5th Embodiment. It is a figure which shows the mode of the board | substrate in each process of the substrate processing which concerns on 5th Embodiment.

  In the following description, a substrate means a semiconductor substrate, a glass substrate for photomask, a glass substrate for liquid crystal display, a glass substrate for plasma display, a substrate for FED (Field Emission Display), a substrate for optical disk, a substrate for magnetic disk, and a magneto-optical substrate. Various substrates such as disk substrates.

  In the following description, a substrate on which a circuit pattern or the like (hereinafter referred to as “pattern”) is formed only on one main surface will be used as an example. Here, the main surface on which the pattern is formed is referred to as “front surface”, and the main surface on which the pattern on the opposite side is not formed is referred to as “back surface”. Further, the surface of the substrate directed downward is referred to as “lower surface”, and the surface of the substrate directed upward is referred to as “upper surface”. In the following description, the upper surface is the surface.

  Embodiments of the present invention will be described below with reference to the drawings, taking a substrate processing apparatus used for processing a semiconductor substrate as an example. Note that the present invention is not limited to the processing of semiconductor substrates, and can also be applied to processing of various substrates such as glass substrates for liquid crystal displays.

<First Embodiment>
FIG. 1 is a schematic side view of a longitudinal section showing an internal configuration of a substrate processing apparatus 1a according to the first embodiment. FIG. 2 is a schematic plan view showing the internal configuration of the substrate processing apparatus 1a according to the first embodiment. In order to clarify the directional relationship between the drawings, XYZ orthogonal coordinate axes are appropriately displayed in the drawings. In the first embodiment, the XY plane is a horizontal plane, and the + Z direction is vertically upward.

  The substrate processing apparatus 1a performs cleaning for removing contaminants such as particles (hereinafter referred to as “particles”) adhering to a substrate W such as a semiconductor substrate (hereinafter simply referred to as “substrate W”). 1 is a single-wafer type substrate processing apparatus used for drying processing after processing and cleaning processing.

  1 and 2 do not show a cleaning nozzle or the like used for the cleaning process, and only a portion used for the drying process is shown, but the substrate processing apparatus 1a may be provided with a cleaning nozzle or the like. good.

<1-1. Configuration of substrate processing apparatus>
The configuration of the substrate processing apparatus 1a will be described with reference to FIGS. The substrate processing apparatus 1a is held in a chamber 11 that is a container for storing a substrate W, a substrate holding unit 15 that holds the substrate W, a control unit 13 that controls each part of the substrate processing apparatus 1a, and a substrate holding unit 15. A dry auxiliary liquid supply means 21 for supplying a dry auxiliary liquid containing a dry auxiliary substance to the substrate W to be held, an IPA supply means 31 for supplying IPA to the substrate W held by the substrate holding means 15, and a substrate holding means 15. Gas supply means 41 for supplying gas to the substrate W to be supplied, suction means 51 for sucking a solid dry auxiliary substance from the surface Wf of the substrate W, and substrate W held by the substrate holding means 15, The anti-scattering cup 12 that collects the IPA discharged from the peripheral edge of W, the drying auxiliary liquid, and the like, and the arms that will be described later of each part of the substrate processing apparatus 1a are independently rotated and driven up and down. It includes an elevation driving section 14, a pressure reducing means 71 for reducing the pressure inside the chamber 11.

  The substrate processing apparatus 1a includes a substrate carry-in / out means (not shown), a chuck pin opening / closing mechanism (not shown), and a wet cleaning means (not shown). Each part of the substrate processing apparatus 1a will be described below.

  The substrate holding unit 15 includes a rotation driving unit 151, a spin base 152, and a chuck pin 153. The spin base 152 has a slightly larger planar size than the substrate W, and a plurality of chuck pins 153 that hold the peripheral portion of the substrate W are erected in the vicinity of the peripheral portion. Three or more chuck pins 153 may be provided to securely hold the circular substrate W. In the first embodiment, three chuck pins 153 are arranged at equal intervals along the peripheral edge of the spin base 152 (see FIG. 2). ). Each chuck pin 153 includes a substrate support pin that supports the peripheral edge of the substrate W from below, and a substrate holding pin that holds the substrate W by pressing the outer peripheral end surface of the substrate W supported by the substrate support pin. Each chuck pin 153 can be switched between a pressing state in which the substrate holding pin presses the outer peripheral end surface of the substrate W and a released state in which the substrate holding pin is separated from the outer peripheral end surface of the substrate W. State switching is executed in accordance with an operation command from the control unit 13 that controls the whole.

  More specifically, when the substrate W is carried into and out of the spin base 152, each chuck pin 153 is released, and when performing substrate processing from cleaning processing to sublimation processing, which will be described later, on the substrate W. Each chuck pin 153 is in a pressed state. When the chuck pin 153 is in a pressed state, the chuck pin 153 grips the peripheral edge of the substrate W, and the substrate W is held in a horizontal posture (XY plane) at a predetermined interval from the spin base 152. As a result, the substrate W is held horizontally with its surface Wf facing upward.

  As described above, in the first embodiment, the substrate W is held by the spin base 152 and the chuck pins 153, but the substrate holding method is not limited to this. For example, the back surface Wb of the substrate W is formed on the spin chuck or the like. You may make it hold | maintain by this adsorption | suction system.

  The spin base 152 is connected to the rotation driving unit 151. The rotation driving unit 151 rotates around the axis A1 along the Z direction according to the operation command of the control unit 13. The rotation drive unit 151 includes a known belt, a motor, and a rotation shaft. When the rotation driving unit 151 rotates around the axis A 1, the substrate W held by the chuck pins 153 above the spin base 152 rotates around the axis A 1 together with the spin base 152.

  Next, the drying auxiliary liquid supply means 21 will be described.

  The drying auxiliary liquid supply means 21 is a unit that supplies the drying auxiliary liquid to the substrate W, and includes a nozzle 22, an arm 23, a pivot shaft 24, a pipe 25, a valve 26, and a drying auxiliary liquid tank 27. Prepare.

  FIG. 4 is a diagram showing a schematic configuration of the drying auxiliary liquid tank 27. The drying auxiliary liquid tank 27 includes a liquid storage unit 271 that stores the drying auxiliary liquid, and a temperature adjustment unit 272 that adjusts the temperature of the drying auxiliary liquid stored in the liquid storage unit 271. The temperature adjustment unit 272 is electrically connected to the control unit 13, and heats or cools the liquid storage unit 271 according to an operation command of the control unit 13, so that the temperature of the drying auxiliary liquid becomes equal to or higher than the melting point of the drying auxiliary substance. Make adjustments.

  For the temperature adjustment unit 272, a known temperature adjustment mechanism such as a resistance heater, a Peltier element, or a pipe through which the temperature is adjusted can be used.

  Returning to FIG. The drying auxiliary liquid tank 27 (more specifically, the liquid storage unit 271) is connected to the nozzle 22 via a pipe 25, and a valve 26 is inserted in the path of the pipe 25. The dry auxiliary liquid in the dry auxiliary liquid tank 27 is pressurized by a pump (not shown), and the dry auxiliary liquid is sent from the pipe 25 toward the nozzle 22.

  The valve 26 is electrically connected to the control unit 13 and is normally closed. The opening / closing of the valve 26 is controlled by the operation command of the control unit 13. When the valve 26 is opened by the operation command of the control unit 13, the drying auxiliary liquid is supplied from the nozzle 22 to the surface Wf of the substrate W through the pipe 25.

  The nozzle 22 is attached to the tip of the arm 23 that extends horizontally, and is disposed above the spin base 152. The rear end portion of the arm 23 is rotatably supported around the axis J1 by a pivot shaft 24 extending in the Z direction, and is supported by the pivot shaft 24 so as to be movable up and down along the axis J1. The pivot shaft 24 is fixed in the chamber 11. The arm 23 is connected to the swing raising / lowering drive unit 14 via the swing shaft 24. The swivel raising / lowering drive unit 14 is electrically connected to the control unit 13, rotates the arm 23 around the axis J1 according to an operation command from the control unit 13, and moves up and down along the axis J1. As the arm 23 moves, the nozzle 22 also moves.

  As indicated by a solid line in FIG. 2, the nozzle 22 is normally disposed outside the peripheral edge of the substrate W and at the retracted position P <b> 1 outside the scattering prevention cup 12. When the arm 23 is rotated by the operation command of the control unit 13, the nozzle 22 moves along the path indicated by the arrow AR1, and is disposed at a position above the central portion (axis A1 or the vicinity thereof) of the surface Wf of the substrate W.

  In the first embodiment, the drying auxiliary substance is preferably a substance having a freezing point and a melting point at 0 ° C. or more and 30 ° C. or less and exhibiting sublimation property under atmospheric pressure. Specifically, 1,1,2,2,3,3,4-heptafluorocyclopentane is used. The substance is a hydrofluorocarbon-based compound (that is, a compound composed of carbon, fluorine and hydrogen) and has a five-membered ring structure. The structural formula is shown in Chemical Formula 1.

  1,1,2,2,3,3,4-heptafluorocyclopentane has a surface tension of 19.6 mN / m in an environment of 25 degrees Celsius, and a vapor pressure of 8.2 kPa in an environment of 20 degrees Celsius ( 62.0 mmHg), a melting point and a freezing point of 20.5 degrees Celsius, and a specific gravity of 1.58 in an environment of 25 degrees Celsius. Since this substance is excellent in solubility of, for example, a fluorine-based polymer, it is used as a solvent for various coating agents and as a cleaning agent for oil film stains.

  In addition, the drying auxiliary liquid in 1st Embodiment melt | dissolves 1,1,2,2,3,3,4-heptafluorocyclopentane. If the environment in which the substrate processing apparatus 1a is installed is an environment where the temperature is higher than the melting point of 1,1,2,2,3,3,4-heptafluorocyclopentane, for example, 25 degrees Celsius, heating is performed. A drying auxiliary liquid can be obtained without any problems. In the first embodiment, the liquid adjusting unit 272 is heated by the temperature adjusting unit 272, and the temperature adjustment is performed so that the drying auxiliary liquid has a temperature equal to or higher than the melting point of the drying auxiliary substance, but this configuration is essential for the implementation of the present invention. If the installation environment of the substrate processing apparatus 1a is an environment whose temperature is higher than the melting point of 1,1,2,2,3,3,4-heptafluorocyclopentane, the temperature adjustment unit 272 may be omitted. good.

  In the first embodiment of the present application, DIW (freezing point: 0 degree Celsius), tertiary butanol (freezing point: 25 degree Celsius), or a mixture thereof can be used as the drying auxiliary substance. In this case, the drying auxiliary liquid is DIW or tertiary butanol in a molten state.

  Returning to FIG. Next, the IPA supply means 31 will be described. The IPA supply means 31 is a unit that supplies IPA (isopropyl alcohol) to the substrate W, and includes a nozzle 32, an arm 33, a pivot shaft 34, a pipe 35, a valve 36, and an IPA tank 37.

  The IPA tank 37 is connected to the nozzle 32 via a pipe 35, and a valve 36 is inserted in the path of the pipe 35. IPA is stored in the IPA tank 37, and the IPA in the IPA tank 37 is pressurized by a pump (not shown) and sent from the pipe 35 toward the nozzle 32.

  The valve 36 is electrically connected to the control unit 13 and is normally closed. The opening / closing of the valve 36 is controlled by the operation command of the control unit 13. When the valve 36 is opened by the operation command of the control unit 13, IPA is supplied from the nozzle 32 to the surface Wf of the substrate W through the pipe 35.

  The nozzle 32 is attached to the tip of the arm 33 that extends horizontally, and is disposed above the spin base 152. The rear end portion of the arm 33 is rotatably supported around the axis J2 by a pivot shaft 34 extending in the Z direction, and is supported by the pivot shaft 34 so as to be movable up and down along the axis J2. The pivot shaft 34 is fixed in the chamber 11. The arm 33 is connected to the swing raising / lowering drive unit 14 via the swing shaft 34. The swivel raising / lowering drive unit 14 is electrically connected to the control unit 13, rotates the arm 33 around the axis J2 according to an operation command from the control unit 13, and moves up and down along the axis J2. As the arm 33 moves, the nozzle 32 also moves.

  As indicated by a solid line in FIG. 2, the nozzle 32 is normally disposed outside the peripheral edge of the substrate W and at the retracted position P <b> 2 outside the scattering prevention cup 12. When the arm 33 is rotated by an operation command from the control unit 13, the nozzle 32 moves along the path indicated by the arrow AR2, and is disposed at a position above the central portion (axis A1 or the vicinity thereof) of the surface Wf of the substrate W.

  In the first embodiment, IPA is used in the IPA supply means 31. However, the present invention may be implemented as long as it is a liquid that is soluble in dry auxiliary substances and deionized water (DIW). , Not limited to IPA. As an alternative to IPA in the first embodiment, methanol, ethanol, acetone, benzene, carbon tetrachloride, chloroform, hexane, decalin, tetralin, acetic acid, cyclohexanol, ether, hydrofluoroether or the like can be given. It is done.

  Returning to FIG. Next, the gas supply means 41 will be described. The gas supply means 41 is a unit that supplies gas to the substrate W, and includes a nozzle 42, an arm 43, a turning shaft 44, a pipe 45, a valve 46, and a gas tank 47.

  FIG. 5 is a diagram showing a schematic configuration of the gas tank 47. The gas tank 47 includes a gas storage unit 471 that stores gas, a temperature adjustment unit 472 that adjusts the temperature of the gas stored in the gas storage unit 471, and a flow rate adjustment unit 473 that adjusts the flow rate of the gas sent to the pipe 45. And having.

  The temperature adjustment unit 472 is electrically connected to the control unit 13 and heats or cools the gas storage unit 471 according to an operation command from the control unit 13. Thereby, temperature adjustment is performed so that the gas stored in the gas storage unit 471 has a predetermined temperature lower than the freezing point and the melting point of the drying auxiliary substance. For the temperature adjustment unit 472, a known temperature adjustment mechanism such as a Peltier element or a pipe through which water whose temperature has been adjusted can be used.

  The flow rate adjustment unit 473 is electrically connected to the control unit 13 and adjusts the flow rate of the gas sent from the gas storage unit 471 to the pipe 45 according to the operation command of the control unit 13 to a predetermined flow rate. A known mass flow controller can be used for the flow rate adjusting unit 473. Further, a pressure regulator may be used as the flow rate adjustment unit 473 for simple flow rate adjustment.

  Returning to FIG. The gas tank 47 (more specifically, the gas storage unit 471) is connected to the nozzle 42 via a pipe 45, and a valve 46 is inserted in the middle of the path of the pipe 45. The gas in the gas tank 47 is pressurized by a pressurizing means (not shown) and sent to the pipe 45. The pressurizing means can be realized by compressing and storing gas in the gas tank 47 in addition to pressurization by a pump or the like, and therefore any pressurizing means may be used.

  The valve 46 is electrically connected to the control unit 13 and is normally closed. The opening / closing of the valve 46 is controlled by the operation command of the control unit 13. When the valve 46 is opened by the operation command of the control unit 13, the gas is supplied from the nozzle 42 to the surface Wf of the substrate W through the pipe 45.

  The nozzle 42 is attached to the tip end portion of the arm 43 that extends horizontally, and is disposed above the spin base 152. The rear end portion of the arm 43 is rotatably supported around the axis J3 by a pivot shaft 44 extending in the Z direction, and is supported by the pivot shaft 44 so as to be movable up and down along the axis J3. The pivot 44 is fixed in the chamber 11. The arm 43 is connected to the swivel raising / lowering drive unit 14 via the swivel shaft 44. The swivel raising / lowering drive unit 14 is electrically connected to the control unit 13, rotates the arm 43 around the axis J3 according to an operation command from the control unit 13, and moves up and down along the axis J3. As the arm 43 moves, the nozzle 42 also moves.

  As indicated by a solid line in FIG. 2, the nozzle 42 is normally disposed outside the peripheral edge of the substrate W and at the retracted position P3 outside the scattering prevention cup 12. When the arm 43 is rotated by an operation command from the control unit 13, the nozzle 42 moves along the path indicated by the arrow AR3, and is disposed at a position above the central portion (axis A1 or the vicinity thereof) of the surface Wf of the substrate W.

  The gas used in the first embodiment is a gas that is inert to the drying auxiliary substance, and more specifically, nitrogen gas. The nitrogen gas used in the first embodiment has a temperature lower than the freezing point and melting point of the drying auxiliary substance. Specifically, when the drying auxiliary substance is 1,1,2,2,3,3,4-heptafluorocyclopentane, it is 0 degree Celsius or more and 15 degrees Celsius or less, and in the first embodiment, 7 degree Celsius. Using nitrogen gas. If nitrogen gas having a temperature lower than 0 degrees Celsius is used, the water vapor present in the chamber 11 solidifies and adheres to the surface Wf of the substrate W, which may adversely affect the substrate W. The nitrogen gas is preferably used.

  The nitrogen gas used in the first embodiment is preferably a dry gas having a dew point of 0 degrees Celsius or less, and the partial pressure of the dry auxiliary substance in the gaseous state contained in the nitrogen gas is: It is lower than the saturated vapor pressure at the temperature of the nitrogen gas of the dry auxiliary substance in the gaseous state. That is, when the nitrogen gas used in the first embodiment is sprayed onto the solid dry auxiliary substance under an atmospheric pressure environment, the dry auxiliary substance can be sublimated into the nitrogen gas.

  In the first embodiment, nitrogen gas is used as the gas supplied by the gas supply means 41, but the implementation of the present invention is not limited to this as long as the gas is inert with respect to the drying auxiliary substance. In the first embodiment, examples of the gas that can replace nitrogen gas include argon gas, helium gas, and air (a gas having a nitrogen gas concentration of 80% and an oxygen gas concentration of 20%). Or the mixed gas which mixed these multiple types of gas may be sufficient.

  Returning to FIG. Next, the decompression means 71 will be described. The decompression unit 71 is a unit that decompresses the interior of the chamber 11 to an environment lower than the atmospheric pressure, and includes an exhaust pump 72, a pipe 73, and a valve 74. The exhaust pump 72 is a known pump that is connected to the chamber 11 via a pipe 73 and applies pressure to the gas. The exhaust pump 72 is electrically connected to the control unit 13 and starts to be driven when the substrate processing apparatus 1a is turned on, and is always in a driving state. The drive of the exhaust pump 72 is controlled by the operation command of the control unit 13. A valve 74 is inserted into the pipe 73. The valve 74 is electrically connected to the control unit 13 and is normally closed. The opening / closing of the valve 74 is controlled by the operation command of the control unit 13.

  When the valve 74 is opened by the operation command of the control unit 13, the gas existing inside the chamber 11 is exhausted to the outside of the chamber 11 through the pipe 73 by the exhaust pump 72.

  Next, the suction means 51 will be described. The suction means 51 is a unit that sucks a solid dry auxiliary substance on the surface Wf of the substrate W, and includes a nozzle 52, an arm 53, a turning shaft 54, a pipe 55, and a valve 56.

  The pipe 55 has one end connected to the nozzle 52 and the other end connected to the exhaust pump 72 of the decompression means 71. That is, the exhaust pump 72 is connected to the nozzle 52 via the pipe 55 in addition to the pipe 73. A valve 56 is inserted in the course of the pipe 55. The valve 56 is electrically connected to the control unit 13 and is normally closed. The opening / closing of the valve 56 is controlled by the operation command of the control unit 13. When the valve 56 is opened by the operation command of the control unit 13, gas or the like is sucked from the nozzle 52 by the exhaust pump 72.

  The nozzle 52 is attached to the tip of the arm 53 that extends horizontally, and is disposed above the spin base 152. The rear end portion of the arm 53 is rotatably supported around the axis J4 by a swing shaft 54 extending in the Z direction, and is supported by the swing shaft 54 so as to be movable up and down along the axis J4. The pivot shaft 54 is fixed in the chamber 11. The arm 53 is connected to the swing raising / lowering drive unit 14 via the swing shaft 54. The swivel raising / lowering drive unit 14 is electrically connected to the control unit 13, rotates the arm 53 around the axis J <b> 4 according to an operation command from the control unit 13, and moves up and down along the axis J <b> 4. As the arm 53 moves, the nozzle 52 also moves.

  As indicated by a solid line in FIG. 2, the nozzle 52 is normally disposed outside the peripheral edge of the substrate W and at the retracted position P <b> 4 outside the scattering prevention cup 12. When the arm 53 is rotated by the operation command of the control unit 13, the nozzle 52 moves along the path indicated by the arrow AR4, and is disposed at a position above the central portion (axis A1 or the vicinity thereof) of the surface Wf of the substrate W. A state in which the nozzle 52 is arranged at a position above the center of the surface Wf is indicated by a broken line in FIG.

  The anti-scattering cup 12 is provided so as to surround the spin base 152. The anti-scattering cup 12 is connected to an elevating drive mechanism (not shown) and can elevate in the Z direction. When supplying the drying auxiliary liquid or IPA to the substrate W, the scattering prevention cup 12 is positioned at a predetermined position as shown in FIG. 1 by the elevating drive mechanism, and the substrate W held by the chuck pin 153 is moved from the side position. surround. Thereby, liquids, such as drying auxiliary liquid and IPA which scatter from substrate W or spin base 152, can be collected.

  FIG. 3 is a schematic diagram showing the configuration of the control unit 13. The control unit 13 is electrically connected to each part of the substrate processing apparatus 1a (see FIG. 1 and the like), and controls the operation of each part. The control unit 13 is configured by a computer having an arithmetic processing unit 16 and a memory 17. As the arithmetic processing unit 16, a CPU that performs various arithmetic processes is used. The memory 17 includes a ROM that is a read-only memory that stores basic programs, a RAM that is a readable and writable memory that stores various types of information, and a magnetic disk that stores control software and data. The magnetic disk stores in advance substrate processing conditions corresponding to the substrate W as a substrate processing program 18 (also called a recipe). The CPU reads the contents into the RAM, and the substrate processing program 18 read into the RAM reads the contents of the substrate processing program 18. The CPU controls each part of the substrate processing apparatus 1a according to the contents.

<1-2. Substrate processing process>
Next, the substrate processing operation in the substrate processing apparatus 1a configured as described above will be described. Here, an uneven pattern Wp is formed on the substrate W by the previous process. The pattern Wp includes a convex portion Wp1 and a concave portion Wp2. In 1st Embodiment, convex part Wp1 is the height of the range of 100-600 nm, and is the width | variety of the range of 10-50 nm. Further, the shortest distance between the two adjacent convex portions Wp1 (the shortest width of the concave portion Wp2) is in the range of 10 to 50 nm. The aspect ratio of the convex portion Wp1, that is, the value obtained by dividing the height by the width (height / width) is 10 to 20. In the present invention, the size of the pattern Wp is not limited to this, and the present invention can also be applied to a substrate W having a pattern of a size other than this.

  Hereinafter, the substrate processing steps will be described with reference to FIGS. FIG. 6 is a flowchart showing the operation of the substrate processing apparatus 1a according to the first embodiment. FIG. 7 is a schematic diagram showing the state of the substrate W in each step of FIG.

  Each drawing from (a) to (e) in FIG. 7 is processed under an atmospheric pressure environment unless otherwise specified. Here, the atmospheric pressure environment refers to an environment of 0.7 atmospheric pressure or higher and 1.3 atmospheric pressure or lower with a standard atmospheric pressure (1 atmospheric pressure, 1013 hPa) as a center. In particular, when the substrate processing apparatus 1a is disposed in a clean room having a positive pressure, the environment of the surface Wf of the substrate W becomes higher than 1 atmosphere.

  Please refer to FIG. First, an execution instruction is issued by the operator for a substrate processing program 18 corresponding to a predetermined substrate W. Thereafter, in preparation for carrying the substrate W into the substrate processing apparatus 1a, the control unit 13 issues an operation command and performs the following operations.

  That is, the rotation of the rotation driving unit 151 is stopped, and the chuck pin 153 is positioned at a position suitable for delivery of the substrate W. Further, the valves 26, 36, 46, 56, 74 are closed, and the nozzles 22, 32, 42, 52 are positioned at the retracted positions P1, P2, P3, P4, respectively. Then, the chuck pin 153 is opened by an opening / closing mechanism (not shown).

  When an unprocessed substrate W is loaded into the substrate processing apparatus 1a by a substrate loading / unloading mechanism (not shown) and placed on the chuck pin 153, the chuck pin 153 is closed by an opening / closing mechanism (not shown).

  After the unprocessed substrate W is held by the substrate holding means 15, a cleaning step S11 is performed on the substrate by a wet cleaning means (not shown). Examples of the wet cleaning process include SC-1 (a liquid containing ammonia, hydrogen peroxide solution, and water) and SC-2 (a liquid containing hydrochloric acid, hydrogen peroxide solution, and water) on the surface of the substrate W. And a step of supplying DIW as a stop solution for the cleaning reaction.

  In the first embodiment, SC-1 is supplied to the surface of the substrate W by a wet cleaning means (not shown), and after cleaning the substrate W, DIW is supplied to the surface Wf of the substrate W. 1 is removed.

  Next, a rinsing step S12 for supplying IPA as a rinsing liquid to the surface Wf of the substrate W on which DIW is adhered is performed. First, the control unit 13 issues an operation command to the rotation drive unit 151 to rotate the substrate W around the axis A1 at a constant speed. At this time, the rotation speed of the substrate W is set to a speed at which the IPA can form a film having a predetermined thickness higher than the convex portion Wp1 over the entire surface Wf.

  Next, the control unit 13 issues an operation command to the swivel raising / lowering drive unit 14 to position the nozzle 32 at the center of the surface Wf of the substrate W. Then, the control unit 13 issues an operation command to the valve 36 to open the valve 36. Thereby, IPA is supplied from the IPA tank 37 to the surface Wf of the substrate W through the pipe 35 and the nozzle 32.

  The IPA supplied to the surface Wf of the substrate W flows from the vicinity of the center of the surface Wf of the substrate W toward the peripheral edge of the substrate W due to the centrifugal force generated by the rotation of the substrate W, and the entire surface of the surface Wf of the substrate W To spread. Thereby, DIW adhering to the surface Wf of the substrate W is removed by supplying IPA, and the entire surface Wf of the substrate W is covered with IPA. After completion of the rinsing step S12, the control unit 13 issues an operation command to the valve 36 and closes the valve 36. Further, the control unit 13 issues an operation command to the turning up / down drive unit 14 to position the nozzle 32 at the retracted position P2.

  FIG. 7A shows the state of the substrate W at the end of the rinsing step S12. As shown in FIG. 7A, the surface Wf of the substrate W on which the pattern Wp (the plurality of convex portions Wp1 and the concave portion Wp2) is formed has the IPA (indicated by “60” in the drawing) supplied in the rinsing step S12. Attached). In other words, the IPA 60 covers the entire surface Wf of the substrate W with a predetermined film thickness. The DIW is replaced by the IPA 60 and removed from the surface Wf of the substrate W.

  Returning to FIG. Next, a drying auxiliary liquid supply step S13 is performed to supply a drying auxiliary liquid obtained by melting the drying auxiliary substance to the surface Wf of the substrate W to which the IPA 60 is attached. First, the control unit 13 issues an operation command to the rotation drive unit 151 to rotate the substrate W around the axis A1 at a constant speed. At this time, the rotation speed of the substrate W is set to a speed at which the drying auxiliary liquid can form a film having a predetermined thickness higher than the convex portion Wp1 on the entire surface Wf.

  Subsequently, the control unit 13 issues an operation command to the swivel raising / lowering drive unit 14 to position the nozzle 22 at the center of the surface Wf of the substrate W. Then, the control unit 13 issues an operation command to the valve 26 to open the valve 26. Thereby, the drying auxiliary liquid is supplied from the drying auxiliary liquid tank 27 to the surface Wf of the substrate W through the pipe 25 and the nozzle 22.

  The drying auxiliary liquid supplied to the surface Wf of the substrate W flows from the vicinity of the center of the surface Wf of the substrate W toward the peripheral portion of the substrate W due to the centrifugal force generated by the rotation of the substrate W, and the surface Wf of the substrate W Diffuses across the surface. Thereby, IPA adhering to the surface Wf of the substrate W is removed by supplying the drying auxiliary liquid, and the entire surface Wf of the substrate W is covered with the drying auxiliary liquid. After completion of the drying auxiliary liquid supply step S13, the control unit 13 issues an operation command to the valve 26 and closes the valve 26. In addition, the control unit 13 issues an operation command to the turning up / down drive unit 14 to position the nozzle 22 at the retracted position P1.

  FIG. 7B shows the state of the substrate W at the end of the drying auxiliary liquid supply step S13. As shown in FIG. 7B, on the surface Wf of the substrate W on which the pattern Wp is formed, the drying auxiliary liquid (indicated by “61” in the drawing) supplied in the drying auxiliary liquid supply step S13 is The IPA 60 is attached and is replaced by the drying auxiliary liquid 61 and removed from the surface Wf of the substrate W. In other words, the drying auxiliary liquid 61 covers the entire surface Wf of the substrate W with a predetermined film thickness.

  Returning to FIG. Next, a solidification step S14 is performed in which the drying auxiliary liquid 61 supplied to the surface Wf of the substrate W is solidified to form a solidified film (that is, a solidified film) of the drying auxiliary substance. First, the control unit 13 issues an operation command to the rotation drive unit 151 to rotate the substrate W around the axis A1 at a constant speed. At this time, the rotation speed of the substrate W is set to a speed at which the drying auxiliary liquid can form a film having a predetermined thickness higher than the convex portion Wp1 on the entire surface Wf.

  Subsequently, the control unit 13 issues an operation command to the swivel raising / lowering drive unit 14 to position the nozzle 42 at the center of the surface Wf of the substrate W. Then, the control unit 13 issues an operation command to the valve 46 to open the valve 46. As a result, gas (nitrogen gas at 7 degrees Celsius in the first embodiment) is supplied from the gas tank 47 to the surface Wf of the substrate W through the pipe 45 and the nozzle 42.

  The gas supplied toward the surface Wf of the substrate W flows from the vicinity of the center of the surface Wf of the substrate W toward the peripheral edge of the substrate W by the centrifugal force generated by the rotation of the substrate W, and the drying auxiliary liquid 61. It diffuses over the entire surface Wf of the substrate W covered with. Thereby, the drying auxiliary liquid 61 adhering to the surface Wf of the substrate W is cooled and solidified at a temperature lower than the freezing point of the drying auxiliary substance, and changes to a solid state. Then, the entire surface Wf of the substrate W is covered with a solidified film of a drying auxiliary substance. That is, in the first embodiment, the solidification step S <b> 14 is a step of solidifying by cooling the drying auxiliary liquid 61 containing the melted drying auxiliary substance, and the gas supply unit 41 corresponds to the “solidification unit”.

  After completion of the solidification step S14, the control unit 13 issues an operation command to the valve 46 to close the valve 46. Further, the control unit 13 issues an operation command to the turning up / down drive unit 14 to position the nozzle 42 at the retracted position P3.

  FIG.7 (c) has shown the mode of the board | substrate W in the middle of solidification process S14. As shown in FIG. 7C, the drying auxiliary liquid 61 supplied in the drying auxiliary liquid supply step S13 is cooled and solidified by the supply of nitrogen gas at 7 degrees Celsius, and a solidified film of the drying auxiliary substance (in the drawing) (Denoted by “62”).

  Returning to FIG. Next, a solid removal step S15 is performed in which the solidified film 62 (that is, the solid dry auxiliary substance) formed on the surface Wf of the substrate W is removed from the surface Wf of the substrate W while maintaining the solid state. When the solid removal step S15 is started, first, the control unit 13 issues an operation command to the rotation drive unit 151 to rotate the substrate W around the axis A1 at a constant speed. At this time, the rotation speed of the substrate W corresponds to the speed at which the nozzle 52 scans the surface Wf, and is set according to the scanning conditions.

  Subsequently, the control unit 13 issues an operation command to the swivel lifting drive unit 14 to position the nozzle 52 at the center of the surface Wf of the substrate W. Further, the control unit 13 issues an operation command to the swivel raising / lowering drive unit 14 and lowers the arm 53 to position the nozzle 52 at a position close to the solidified film 62 formed on the surface Wf of the substrate W. Then, the control unit 13 issues an operation command to the valve 56 and opens the valve 56. As a result, suction from the nozzle 52 is performed, and a solid-state drying auxiliary substance located at a position close to the nozzle 52 in the solidified film 62 on the surface Wf of the substrate W is sucked into the nozzle 52 and the surface of the substrate W It is removed from Wf in a solid state.

  In addition, the control unit 13 issues an operation command to the swivel raising / lowering drive unit 14 and moves the nozzle 52 during the suction operation from the center portion of the substrate W to the peripheral portion of the substrate W along the arrow AR4 (see FIG. 2). Let That is, the nozzle 52 is scanned (scanned) from the central portion of the substrate W to the peripheral portion of the substrate W. By the scanning of the nozzle 52 and the rotation of the substrate W, the suction position by the nozzle 52 is sequentially positioned over the entire surface Wf of the substrate W. Thereby, the solidified film 62 adhering to the surface Wf of the substrate W is entirely sucked by the nozzle 52 and removed from the surface Wf of the substrate W. In the first embodiment, the suction unit 51 corresponds to the “solid removal unit” of the present invention.

  After completion of the solid removal step S15, the control unit 13 issues an operation command to the valve 56 and closes the valve 56. In addition, the control unit 13 issues an operation command to the turning lift drive unit 14 to position the nozzle 52 at the retracted position P4.

  FIG. 7D shows the state of the substrate W during the solid removal step S15. As shown in FIG. 7D, a part of the solidified film 62 formed in the solidification step S14 is sucked by the nozzle 52 moving along the path indicated by the arrow AR4, so that it is removed in the solid state. The The adhesion force of the solidified film 62 to the surface Wf of the substrate W becomes stronger as it is closer to the surface Wf of the substrate W, and the adhesion force of the solidified film 62 filled in the recess Wp2 to the surface Wf of the substrate W is extremely strong. For this reason, the solidified film 62 cannot be completely removed by the physical force generated by the suction of the nozzle 52, and the solid state drying auxiliary substance located above the solidified film 62 can be removed by the nozzle 52.

  In other words, the solid-state drying auxiliary substance located above the solidified film 62 is removed by the suction means 51 in the solid removal step S15, so that the solidified film 62 is thinned.

  Returning to FIG. Next, a gasification step S16 is performed in which the solidified film 62 formed on the surface Wf of the substrate W is sublimated and removed from the surface Wf of the substrate W. When the gasification step S16 is started, the control unit 13 issues an operation command to the rotation driving unit 151 to rotate the substrate W around the axis A1 at a constant speed. At this time, the rotation speed of the substrate W corresponds to the speed at which the nozzle 42 scans the surface Wf, and is set according to the scanning conditions.

  Subsequently, the control unit 13 issues an operation command to the swivel raising / lowering drive unit 14 to position the nozzle 42 at the center of the surface Wf of the substrate W. Then, the control unit 13 issues an operation command to the valve 46 to open the valve 46. As a result, gas (nitrogen gas at 7 degrees Celsius in the first embodiment) is supplied from the gas tank 47 to the surface Wf of the substrate W through the pipe 45 and the nozzle 42.

  The gas supplied toward the surface Wf of the substrate W flows from the vicinity of the center of the surface Wf of the substrate W toward the periphery of the substrate W due to the centrifugal force generated by the rotation of the substrate W, and is solidified into a thin film. It diffuses over the entire surface Wf of the substrate W covered with the film 62. Here, the partial pressure of the vapor of the dry auxiliary substance in the supplied gas is set lower than the saturated vapor pressure of the dry auxiliary substance at 7 degrees Celsius. Therefore, when such a gas is supplied to the surface Wf of the substrate W, the drying auxiliary substance is sublimated from the solidified film 62 into the gas.

  The control unit 13 further issues an operation command to the swivel raising / lowering drive unit 14, and moves the nozzle 42 during gas supply from the center of the substrate W to the peripheral edge of the substrate W along the arrow AR3 (see FIG. 2). . That is, the nozzle 42 is scanned from the center of the substrate W to the peripheral edge of the substrate W. By the scanning of the nozzle 42 and the rotation of the substrate W, the gas supply position by the nozzle 42 is sequentially positioned over the entire surface Wf of the substrate W. Thereby, the solidified film 62 adhering to the surface Wf of the substrate W is sublimated without being left behind and removed from the surface Wf of the substrate W. In the first embodiment, the gas supply means 41 corresponds to the “gasification means” of the present invention.

  Further, since the gas supplied from the nozzle 42 is at a lower temperature (7 degrees Celsius) than the melting point of the drying auxiliary substance (20.5 degrees Celsius), it prevents the drying auxiliary substance from melting in the coagulated film 62 while in the gas. The solidified film 62 can be sublimated.

  When the drying auxiliary substance on the surface Wf of the substrate W is removed, the solid auxiliary auxiliary substance is sublimated, so that the drying auxiliary substance changes from the solid state to the gas state without going through the liquid state. Can be prevented, and the surface Wf of the substrate W can be satisfactorily dried.

  In the first embodiment, since the solidified film 62 is thinned by performing the solid removal process S15 before the gasification process S16 is executed, the amount of the solidified film 62 to be sublimated in the gasification process S16 is reduced. It is possible to reduce the processing time and gas consumption in the gasification step S16.

  Further, by reducing the amount of the dry auxiliary substance that is in the gaseous state in the gasification step S16 by reducing the thickness of the coagulated film 62, contamination by the dry auxiliary substance in the chamber 11 and various pipes can be suppressed. .

  Furthermore, in the solid removal step S15, a part of the solid-state drying auxiliary substance in the solidified film 62 is externally discharged from the surface Wf of the substrate W through the exhaust pump 72 while being in a solid state by the suction of the nozzle 52. Since it is removed by discharging to the wastewater, it becomes easy to recover the dry auxiliary substance after discharging, and the cost and environmental burden for waste liquid treatment can be reduced.

  Further, in the solid removal step S15, since no liquid or the like that dissolves the solidified film 62 is used, the solidified film 62 can be thinned while preventing the pattern Wp from collapsing.

  FIG. 7E shows the state of the substrate W during the gasification step S16. As shown in FIG. 7E, the coagulation film 62 of the drying auxiliary material formed in the solidification step S14 and thinned in the solid removal step S15 is sublimated by the supply of nitrogen gas at 7 degrees Celsius to form the surface Wf. Has been removed from.

  After completion of the gasification step S16, the control unit 13 issues an operation command to the valve 46, and closes the valve 46. Further, the control unit 13 issues an operation command to the turning up / down drive unit 14 to position the nozzle 42 at the retracted position P3.

  Thus, the drying of the surface Wf of the substrate W is completed, and a series of substrate drying processes is completed. After the substrate drying process as described above, the substrate W after the drying process is carried out of the chamber 11 by a substrate carry-in / out mechanism (not shown).

  As described above, in the first embodiment, the surface of the substrate W on which the IPA is adhered to the drying auxiliary liquid obtained by melting the drying auxiliary substance (1, 1, 2, 2, 3, 3, 4-heptafluorocyclopentane). After being supplied to Wf and coagulating the dry auxiliary liquid on the surface Wf of the substrate W to form a solidified film of the dry auxiliary substance, a part of the solid state dry auxiliary substance remains in the solid state by suction. Remove and thin the coagulated film. Thereafter, the drying auxiliary substance is sublimated and removed from the surface Wf of the substrate W, whereby the substrate W is dried.

  Here, by using 1,1,2,2,3,3,4-heptafluorocyclopentane as a drying auxiliary substance, pattern collapse of the substrate can be more reliably suppressed as compared with conventional substrate drying. effective. As this cause, it is considered that the following causes and other causes are acting in combination.

(Cause 1) 1,1,2,2,3,3,4-Heptafluorocyclopentane has a melting point of 20.5 degrees Celsius and can be supplied in a molten state, so that a uniform solidified film can be formed on the substrate.

(Cause 2) The vapor pressure of 1,1,2,2,3,3,4-heptafluorocyclopentane is 8.2 kPa (20 degrees Celsius), and DIW (vapor pressure 2.3 kPa) in the conventional sublimation drying technique. : 20 degrees Celsius) and tertiary butanol (vapor pressure 4.1 kPa: 20 degrees Celsius), the sublimation process can be performed at a higher sublimation speed than before.

(Cause 3) 1,1,2,2,3,3,4-heptafluorocyclopentane has no OH group and is less soluble in water than tertiary butanol, so mixing with water occurs In addition, no moisture remains between the patterns after sublimation.

  In the first embodiment, in the solidification step S14 and the gasification step S16, the common gas supply unit 41 is used to convert nitrogen gas, which is an inert gas inert to the drying auxiliary substance, into the drying auxiliary substance. Was supplied at a temperature lower than the freezing point. Thereby, since the number of parts used for processing can be reduced, there is an effect that the apparatus cost can be reduced. In particular, in the first embodiment, since the pipe 73 and the valve 74 of the decompression means 71 are not used, the pipe 73 and the valve 74 may be omitted.

Second Embodiment
Next, a second embodiment of the substrate processing apparatus according to the present invention will be described. The main difference between the second embodiment and the first embodiment is that in the gasification step S16, the inside of the chamber 11 is depressurized instead of supplying gas. Even with such a configuration, the surface of the substrate can be dried while suppressing collapse of the pattern.

<2-1. Overall configuration of substrate processing apparatus>
Since the configuration of the second embodiment is basically the same as the substrate processing apparatus 1a shown in FIGS. 1 and 2 which is the configuration of the first embodiment, the same reference numerals are given in the following description and the description of the configuration is omitted. To do.

<2-2. Substrate processing process>
Next, the substrate processing operation of the second embodiment in the substrate processing apparatus 1a configured similarly to the first embodiment will be described.

  Hereinafter, the substrate processing steps will be described with reference to FIGS. 1, 2, and 6 as appropriate. The second embodiment is different from the first embodiment in that the gasification step S16 is performed by decompression in the chamber 11 by the decompression means 71 instead of supplying the gas from the nozzle 42. Since this is the same as that of the first embodiment, description of portions common to the first embodiment will be omitted.

  Please refer to FIG. After the cleaning step S11, the rinsing step S12, the drying auxiliary liquid supply step S13, the solidification step S14, and the solid removal step S15 are performed, the solidified film 62 formed on the surface Wf of the substrate W is sublimated, and the substrate W A gasification step S16 for removing from the surface Wf is performed. When the gasification step S <b> 16 is started, the decompression process in the chamber 11 by the decompression unit 71 is started based on the operation command of the control unit 13.

  That is, the control unit 13 issues an operation command to the valve 74 to open the valve 74. Thereby, the gas inside the chamber 11 is exhausted to the outside of the chamber 11 through the pipe 73. At this time, all the valves 26, 36, 46, and 56 are closed, and the inside of the chamber 11 is hermetically sealed except for the pipe 73, whereby the internal environment of the chamber 11 is reduced from the atmospheric pressure.

  By the decompression process, the environment in the chamber 11 becomes a pressure lower than the saturation vapor pressure of the drying auxiliary substance. Therefore, when such a reduced pressure environment is maintained, the drying auxiliary substance is sublimated from the coagulation film 62.

  When sublimation of the drying auxiliary substance occurs from the solidified film 62, the drying auxiliary substance that changes from a solid state to a gas state takes heat from the solidified film 62 as sublimation heat, and thus the solidified film 62 is cooled. Therefore, in the second embodiment, the gasification step S16 separately cools the solidified film 62 even when the environment in the chamber 11 is 25 degrees Celsius (normal temperature environment) slightly higher than the melting point of the drying auxiliary substance. The solidified film 62 can be maintained at a temperature lower than the melting point of the drying auxiliary substance (20.5 degrees Celsius) without causing the solidification film 62 into the gas while preventing the drying auxiliary substance from melting in the solidified film 62. Can be sublimated.

In the second embodiment, the pressure is reduced from atmospheric pressure (about 1 atm, about 1013 hPa) to about 1.7 × 10 ⁻⁵ atm (1.7 Pa). In the implementation of the present invention, the pressure is not limited to the pressure, and the pressure in the chamber 11 after the pressure reduction may be appropriately set according to the pressure resistance of the chamber 11 and the like.

  As described above, in the second embodiment, when the drying auxiliary substance on the surface Wf of the substrate W is removed, the drying auxiliary substance is sublimated so that the drying auxiliary substance does not pass through the liquid state and is gas from the solid state. Since it changes to the state, it is possible to prevent surface tension from acting on the pattern Wp and to dry the surface Wf of the substrate W well.

  Moreover, in 2nd Embodiment, the pressure in the chamber 11 by the pressure reduction means 71 can make the environment in the chamber 11 a pressure lower than the saturated vapor pressure of the drying auxiliary substance. As a result, a substance that does not sublimate under an atmospheric pressure environment can be applied as a drying auxiliary substance, and the range of selection of the drying auxiliary substance can be expanded. In addition, the sublimation speed of the drying auxiliary substance can be increased. The faster the sublimation speed, the more the pattern collapse can be prevented. Therefore, the substrate W can be dried more reliably while preventing the pattern collapse.

  In addition, the second embodiment has an effect obtained by performing the solid removal step S15 as in the first embodiment.

  After the end of the gasification step S16, the control unit 13 issues an operation command to the valve 74 and closes the valve 74. Then, the control unit 13 issues an operation command to the valve 46 and opens the valve 46 to introduce gas (nitrogen gas) from the gas tank 47 into the chamber 11 through the pipe 45 and the nozzle 42. Is returned from the reduced pressure environment to the atmospheric pressure environment. At this time, the nozzle 42 may be positioned at the retracted position P3 or may be positioned at the center of the surface Wf of the substrate W.

  Note that the method for returning the chamber 11 to the atmospheric pressure environment after the gasification step S16 is not limited to the above, and various known methods may be employed.

  Thus, a series of substrate drying processes are completed. After the substrate drying process as described above, the substrate W after the drying process is carried out of the chamber 11 by a substrate carry-in / out mechanism (not shown).

<Third Embodiment>
Next, a third embodiment of the substrate processing apparatus according to the present invention will be described. The main difference between the third embodiment and the first embodiment is that, in the solid removal step S15, instead of suction by the nozzle 52, a part of the solidified film 62 is blown off and removed by gas injection. . Even with such a configuration, the surface of the substrate can be dried while suppressing collapse of the pattern.

<3-1. Overall configuration of substrate processing apparatus>
Since the configuration of the third embodiment is basically the same as the substrate processing apparatus 1a shown in FIGS. 1 and 2 which is the configuration of the first embodiment, the same reference numerals are given in the following description and the description of the configuration is omitted. To do. In the third embodiment, since the suction unit 51 and the decompression unit 71 are not used in the substrate processing apparatus 1a, these configurations may be omitted as appropriate.

<3-2. Substrate processing process>
Next, the substrate processing operation of the third embodiment in the substrate processing apparatus 1a configured similarly to the first embodiment will be described.

  Hereinafter, the substrate processing steps will be described with reference to FIGS. 1, 2, and 6 as appropriate. The third embodiment is different from the first embodiment in that the solid removal step S15 is in the solid state by the gas injected from the nozzle 42 of the gas supply means 41 in place of the suction of the solid state dry auxiliary substance by the nozzle 52. Since the other configuration is the same as that of the first embodiment, the description of the parts common to the first embodiment is omitted.

  Please refer to FIG. After the cleaning step S11, the rinsing step S12, the drying auxiliary liquid supply step S13, and the solidification step S14 are executed, some solid state drying auxiliary substances in the solidified film formed on the surface Wf of the substrate W are solidified. A solid removal step S15 is performed in which the solidified film is removed from the surface Wf of the substrate W while the state is maintained.

  In the third embodiment, in the solidification step S14, as in the first embodiment, the nozzle 42 is positioned at the center of the surface Wf of the substrate W, and a gas having a temperature lower than the freezing point of the drying auxiliary substance is supplied. The drying auxiliary liquid formed on the surface Wf of W is solidified to form a solidified film. And unlike 1st Embodiment, after completion | finish of solidification process S14, without closing the valve 46 and positioning the nozzle 42 to the retracted position P3, the nozzle 42 is left as it is at the center portion of the surface Wf of the substrate W. In the state where it is positioned, the subsequent solid removal step S15 is started.

  When the solid removal step S15 is started, the control unit 13 issues an operation command to the flow rate adjusting unit 473 (see FIG. 5) of the gas tank 47, and the flow rate adjusting unit 473 increases the set flow rate to a predetermined flow rate. Thereby, the flow velocity of the gas supplied from the nozzle 42 increases as the flow rate increases. Of the solidified film adhering to the surface Wf of the substrate W, the solid-state drying auxiliary substance located above and far from the surface Wf and having a weak adhesive force with the surface Wf is caused by the gas injected from the nozzle 42. It is blown off from the surface Wf and removed from the surface Wf of the substrate W in a solid state. Thereby, the coagulation film is thinned.

  Further, the control unit 13 issues an operation command to the swivel raising / lowering drive unit 14, and moves the nozzle 42 during gas supply from the center portion of the substrate W to the peripheral portion of the substrate W along the arrow AR3 (see FIG. 2). Let That is, the nozzle 42 is scanned from the center of the substrate W to the peripheral edge of the substrate W. By the scanning of the nozzle 42 and the rotation of the substrate W, the gas supply position by the nozzle 42 is sequentially positioned over the entire surface Wf of the substrate W. As a result, the solidified film adhering to the surface Wf of the substrate W is thinned entirely.

  In 3rd Embodiment, the gas supply means 41 which blows off the dry auxiliary substance of a solid state is equivalent to the "solid removal means" of this invention.

  When the coagulated film is thinned to a predetermined thickness, the gasification step S16 is started. When the gasification step S16 is started, the control unit 13 issues an operation command to the flow rate adjustment unit 473 of the gas tank 47, and the flow rate adjustment unit 473 decreases the set flow rate to another predetermined flow rate. Thereby, the flow velocity of the gas supplied from the nozzle 42 decreases with a decrease in the flow rate. In addition, the control unit 13 issues an operation command to the swivel raising / lowering drive unit 14, and sets the scanning speed of the nozzle 42 along the arrow AR3 to a predetermined speed.

  By the scanning of the nozzle 42 and the rotation of the substrate W, the gas supply position by the nozzle 42 is sequentially positioned over the entire surface Wf of the substrate W. Thereby, the solidified film 62 adhering to the surface Wf of the substrate W is sublimated without being left behind and removed from the surface Wf of the substrate W. In the third embodiment, the gas supply means 41 corresponds to the “gasification means” of the present invention.

  Further, since the gas supplied from the nozzle 42 is at a lower temperature (7 degrees Celsius) than the melting point of the drying auxiliary substance (20.5 degrees Celsius), it prevents the drying auxiliary substance from melting in the coagulated film 62 while in the gas. The solidified film 62 can be sublimated.

  In the third embodiment, similarly to the first embodiment, when the drying auxiliary substance on the surface Wf of the substrate W is removed, the solid auxiliary substance is sublimated so that the drying auxiliary substance does not pass through the liquid state. Since the state changes to the gaseous state, the surface tension can be prevented from acting on the pattern Wp, and the surface Wf of the substrate W can be satisfactorily dried.

  Further, in the third embodiment, the gas supply means 41 is a “solidification means” for solidifying the drying auxiliary liquid in the solidification step S14, and a “solid” for removing the drying auxiliary substance in a solid state by blowing it away in the solid removal step S15. It is used in combination as “removal means” and “gasification means” for changing the drying auxiliary substance from the solid state to the gas state without passing through the liquid state in the gasification step S16.

  Thereby, the number of parts used for processing can be reduced, and the apparatus cost can be reduced. Further, after the solidification step S14, the solid removal step S15 can be performed immediately by increasing the flow rate of the gas injected from the nozzle 42, and the gasification step S16 is subsequently performed. Can contribute to shortening the processing time.

  In the third embodiment, after the solid removal step S15, the gas flow rate is reduced in the flow rate adjusting unit 473 in performing the gasification step S16. However, the implementation of the present invention is not limited to this, and the gasification step is performed. The gas flow rate in step S16 may be equal to the gas flow rate in solid removal step S15.

  However, since the sublimation rate is saturated at a predetermined flow rate even if the gas flow rate is increased, it is not efficient to supply the gas flow rate in the solid removal step S15 as it is in the gasification step S16. Further, at the gas flow rate in the solid removal step S15, a gas having a flow velocity for blowing off the solid-state drying auxiliary substance is supplied from the nozzle 42. Therefore, if the speed is maintained as it is, the gas is physically injected into the pattern Wp by gas injection in the gasification step S16. Damage may occur. For this reason, it is more preferable to reduce the gas flow rate in the gasification step S16 than in the solid removal step S15.

  After completion of the gasification step S16, the control unit 13 issues an operation command to the valve 46, and closes the valve 46. Further, the control unit 13 issues an operation command to the turning up / down drive unit 14 to position the nozzle 42 at the retracted position P3.

  Thus, the drying of the surface Wf of the substrate W is completed, and a series of substrate drying processes is completed. After the substrate drying process as described above, the substrate W after the drying process is carried out of the chamber 11 by a substrate carry-in / out mechanism (not shown).

<Fourth embodiment>
Next, a fourth embodiment of the substrate processing apparatus according to the present invention will be described. The main difference between the fourth embodiment and the first embodiment is that, in the solid removal step S15, instead of suction by the nozzle 52, a part of the coagulation film is washed away with a liquid in which the drying auxiliary substance is hardly soluble. The point is to remove. Even with such a configuration, the surface of the substrate can be dried while suppressing collapse of the pattern.

<4-1. Overall configuration of substrate processing apparatus>
FIG. 8 is a schematic side view of a longitudinal section showing the internal configuration of the substrate processing apparatus 1b according to the fourth embodiment. The substrate processing apparatus 1b of the fourth embodiment is different from the substrate processing apparatus 1a of the first embodiment in that a DIW supply unit 81 is provided instead of the suction unit 51. Since the other configuration is basically the same as that of the substrate processing apparatus 1a shown in FIGS. 1 and 2, the same reference numerals are given in the following description and the description of the configuration is omitted. In the fourth embodiment, since the decompression means 71 is not used in the substrate processing apparatus 1b, the decompression means 71 may be omitted as appropriate.

  The DIW supply unit 81 is a unit that supplies a liquid (in the fourth embodiment, DIW) in which the drying auxiliary substance is sparingly soluble to the substrate W. The nozzle 82, the arm 83, the pivot shaft 84, the pipe 85, and the like. , A valve 86 and a DIW tank 87.

  The DIW tank 87 is a tank that stores DIW. In the DIW tank 87, the temperature of DIW stored by a temperature adjusting unit (not shown) is adjusted to a temperature lower than the melting point of the drying auxiliary substance. In the fourth embodiment, the DIW temperature is maintained at 7 degrees Celsius in the DIW tank 87.

  The DIW tank 87 is connected to the nozzle 82 via a pipe 85, and a valve 86 is inserted midway along the pipe 85. DIW in the DIW tank 87 is pressurized by a pump (not shown), and DIW is sent from the pipe 85 toward the nozzle 82.

  The valve 86 is electrically connected to the control unit 13 and is normally closed. The opening / closing of the valve 86 is controlled by the operation command of the control unit 13. When the valve 86 is opened by the operation command of the control unit 13, DIW is supplied from the nozzle 82 to the surface Wf of the substrate W through the pipe 85.

  The nozzle 82 is attached to the tip of an arm 83 that extends horizontally, and is disposed above the spin base 152. The rear end portion of the arm 83 is rotatably supported around the axis J4 by a pivot shaft 84 extending in the Z direction, and is supported by the pivot shaft 84 so as to be movable up and down along the axis J4. The pivot shaft 84 is fixed in the chamber 11. The arm 83 is connected to the swing raising / lowering drive unit 14 via the swing shaft 84. The swivel raising / lowering drive unit 14 is electrically connected to the control unit 13, rotates the arm 83 about the axis J4 according to an operation command from the control unit 13, and moves up and down along the axis J4. As the arm 83 moves, the nozzle 82 also moves.

  In the present invention, the phrase “drying auxiliary substance is“ slightly soluble ”in a liquid means that the drying auxiliary substance has a solubility in the liquid of 1 g / 100 g liquid or less at 1 atm and 20 degrees Celsius. In the fourth embodiment, 1,1,2,2,3,3,4-heptafluorocyclopentane is used as a drying auxiliary substance, and its solubility in water is 0.072 g / 100 g water. DIW can be said to be a liquid that is sparingly soluble in dry auxiliary substances.

<4-2. Substrate processing process>
Next, the substrate processing operation of the fourth embodiment in the substrate processing apparatus 1b will be described.

  Hereinafter, the substrate processing steps will be described with reference to FIGS. 6 and 8 as appropriate. The substrate processing operation of the fourth embodiment is different from that of the first embodiment in that the solid removal step S15 is discharged from the nozzle 82 of the DIW supply means 81 instead of sucking the solid dry auxiliary substance by the nozzle 52. The other configuration is the same as that of the first embodiment because the solid-state drying auxiliary substance is washed away by DIW, and the description of the parts common to the first embodiment is omitted.

  Please refer to FIG. After the cleaning step S11, the rinsing step S12, the drying auxiliary liquid supply step S13, and the solidification step S14 are executed, some solid state drying auxiliary substances in the solidified film formed on the surface Wf of the substrate W are solidified. A solid removal step S15 is performed in which the solidified film is removed from the surface Wf of the substrate W while the state is maintained.

  When the solid removal step S15 is started, the control unit 13 issues an operation command to the rotation drive unit 151 to rotate the substrate W around the axis A1 at a constant speed. At this time, the rotation speed of the substrate W is set to a speed at which DIW supplied from the nozzle 82 can be swung out from the surface Wf to the outside in the radial direction of the substrate W by centrifugal force.

  Subsequently, the control unit 13 issues an operation command to the swivel raising / lowering drive unit 14 to position the nozzle 82 at the center of the surface Wf of the substrate W. Then, the control unit 13 issues an operation command to the valve 86 to open the valve 86. Thereby, DIW is supplied from the nozzle 82 to the surface Wf of the substrate W.

  The DIW supplied to the surface Wf of the substrate W flows from the vicinity of the center of the surface Wf of the substrate W toward the periphery of the substrate W due to the centrifugal force generated by the rotation of the substrate W, and the entire surface of the surface Wf of the substrate W. To spread. Thereafter, DIW is swung off from the peripheral edge of the substrate W to the outside in the radial direction of the substrate W, collected by the anti-scattering cup 12, and sent to the drainage mechanism.

  Of the solidified film on the surface Wf of the substrate W, the upper dry auxiliary substance that is far from the surface Wf of the substrate W and has a weak adhesion to the surface Wf is pushed away by the DIW supplied from the nozzle 82, The substrate moves along with the DIW toward the periphery of the substrate W, and is removed from the substrate W in the radial direction outside in the solid state. Thereby, the coagulation film is thinned. In the fourth embodiment, the DIW supply unit 81 corresponds to the “solid removal unit” of the present invention.

  Here, in the recess Wp2 of the pattern Wp present on the surface Wf of the substrate W, a solid dry auxiliary substance having a stronger adhesion to the surface Wf is located, so the supplied DIW does not enter the pattern Wp. . In addition, since the drying auxiliary substance is hardly soluble in DIW, there is no possibility that the solidified film is dissolved by the supplied DIW and DIW enters the pattern Wp portion. Further, since DIW of 7 degrees Celsius, which is a temperature lower than the melting point of the drying auxiliary substance, is supplied from the nozzle 82, the solidified film can be thinned while preventing the drying auxiliary substance from melting. As a result, the coagulation film can be thinned while preventing pattern collapse.

  Further, since the drying auxiliary material that has been pushed to the outside in the radial direction of the substrate W together with DIW and collected by the anti-scattering cup 12 remains in a solid state without being dissolved in DIW, it is physically present in the drainage mechanism or the like. By providing a filter (for example, a mesh filter), the drying auxiliary substance can be easily separated from the DIW. For this reason, the cost and environmental burden concerning waste liquid processing etc. can be reduced.

  In the solid removal step S15, when the thinning of the solidified film is completed, for example, after a predetermined time has elapsed since the opening of the valve 86, the control unit 13 issues an operation command to the valve 86 and closes the valve 86. Further, the control unit 13 issues an operation command to the turning up / down drive unit 14 to position the nozzle 82 at the retracted position P4. Then, the control unit 13 issues an operation command to the rotation driving unit 151 to increase the rotation speed of the substrate W, and spin-dry DIW attached to the solidified film on the surface Wf of the substrate W.

  The drying of the DIW after the thinning of the solidified film is not limited to spin drying, and may be dried by supplying gas from the gas supply means 41.

  After the completion of the solid removal step S15, as in the first embodiment, the gas supply means 41 changes the solid dry auxiliary substance into a gas state by sublimation and removes it from the surface Wf of the substrate W.

  Thus, the drying of the surface Wf of the substrate W is completed, and a series of substrate drying processes is completed. After the substrate drying process as described above, the substrate W after the drying process is carried out of the chamber 11 by a substrate carry-in / out mechanism (not shown).

<Fifth Embodiment>
Next, a fifth embodiment of the substrate processing apparatus according to the present invention will be described. The main difference between the fifth embodiment and the first embodiment is that, in the solid removal step S15, instead of suction by the nozzle 52, a scraping means 91 that slides on the solidified film is provided, and above the solidified film. It is in the point which is removed by scraping off the solid-state drying auxiliary substance located in the area. Even with such a configuration, the surface of the substrate can be dried while suppressing collapse of the pattern.

<5-1. Overall configuration of substrate processing apparatus>
FIG. 9 is a schematic side view of a longitudinal section showing the internal configuration of the substrate processing apparatus 1c according to the fifth embodiment. FIG. 10 is a schematic plan view showing the internal configuration of the substrate processing apparatus 1c according to the fifth embodiment. The substrate processing apparatus 1c according to the fifth embodiment is different from the substrate processing apparatus 1a according to the first embodiment in that a scraping unit 91 is provided instead of the suction unit 51. Since the other configuration is basically the same as that of the substrate processing apparatus 1a shown in FIGS. 1 and 2, the same reference numerals are given in the following description and the description of the configuration is omitted. In the fifth embodiment, since the decompression means 71 is not used in the substrate processing apparatus 1c, the decompression means 71 may be omitted as appropriate.

  Please refer to FIG. The scraping unit 91 is a unit that scrapes and removes a part of the solidified film formed on the surface Wf of the substrate W, and includes a blade 92, an arm 93, and a pivot shaft 94. In addition to the above, the scraping unit 91 may include a recovery mechanism for recovering the solidified solid film adhered to the blade 92 and cleaning the blade 92.

  The blade 92 extends at the tip of the horizontally extending arm 93 and is disposed above the spin base 152. The rear end portion of the arm 93 is rotatably supported around the axis J4 by a pivot shaft 94 extending in the Z direction, and is supported by the pivot shaft 94 so as to be movable up and down along the axis J4. The pivot shaft 94 is fixed in the chamber 11. The arm 93 is connected to the swivel raising / lowering drive unit 14 via the swivel shaft 94. The swivel raising / lowering drive unit 14 is electrically connected to the control unit 13, rotates the arm 93 about the axis J4 according to an operation command from the control unit 13, and moves up and down along the axis J4. As the arm 93 moves, the blade 92 also moves.

  As indicated by a solid line in FIG. 10, the blade 92 is normally disposed outside the peripheral edge of the substrate W and at the retracted position P4 outside the scattering prevention cup 12. When the arm 93 is rotated by the operation command of the control unit 13, the blade 92 moves along the path indicated by the arrow AR4, and is disposed at a position above the central portion (axis A1 or the vicinity thereof) of the surface Wf of the substrate W.

  The broken line in FIG. 10 shows a state in which the tip of the arm 93 is disposed above the center portion of the surface Wf, and the blade 92 is disposed along the surface Wf of the substrate W from the center portion of the surface Wf to the radially outer side of the substrate W. Show. As indicated by the broken line, the length of the blade 92 is longer than the diameter of the substrate W. For this reason, if the substrate W rotates once around the axis A1, the entire surface Wf of the substrate W can be slid by the blade 92.

<5-2. Substrate processing process>
Next, the substrate processing operation of the fifth embodiment in the substrate processing apparatus 1c will be described.

  Hereinafter, the substrate processing steps will be described with reference to FIGS. 6, 9, 10 and 11 as appropriate. FIG. 11 is a schematic diagram showing the state of the substrate W in each step of FIG. 6 according to the fifth embodiment. Each figure from (a) to (e) in FIG. 11 is processed under an atmospheric pressure environment unless otherwise specified.

  The substrate processing operation of the fifth embodiment is different from that of the first embodiment in that the solid removal step S15 is replaced with suction of the solid dry auxiliary substance by the nozzle 52, and the solid state by the blade 92 of the scraping means 91 is changed. The other configuration is the same as that of the first embodiment because the drying auxiliary material is scraped off, and therefore, the description of the parts common to the first embodiment is omitted.

  Please refer to FIG. After the cleaning step S11, the rinsing step S12, the drying auxiliary liquid supply step S13, and the solidification step S14 are executed, some solid state drying auxiliary substances in the solidified film formed on the surface Wf of the substrate W are solidified. A solid removal step S15 is performed in which the solidified film is removed from the surface Wf of the substrate W while the state is maintained. 11 (a), 11 (b), and 11 (c) show the state of the substrate W at the end of the rinsing step S12, the end of the drying auxiliary liquid supply step S13, and in the middle of the solidification step S14, respectively. It is a schematic diagram shown. Immediately before the start of the solid removal step S15, a solidified film 62 is formed on the surface Wf of the substrate W as shown in FIG.

  When the solid removal step S15 is started, the control unit 13 issues an operation command to the rotation drive unit 151 to rotate the substrate W around the axis A1 at a constant speed. At this time, the rotation speed of the substrate W is appropriately set according to the condition of the scraping speed at which the blade 92 scrapes the solidified film 62 positioned on the surface Wf of the substrate W. In FIG. 10, the substrate W rotates counterclockwise around the axis A1.

  Subsequently, the control unit 13 issues an operation command to the swivel raising / lowering drive unit 14, turns the arm 93, and positions the blade 92 at the center of the surface Wf of the substrate W (a broken line position in FIG. 10). Then, the control unit 13 issues an operation command to the swivel raising / lowering drive unit 14 and lowers the arm 93 to position the blade 92 at a predetermined height in contact with the solidified film 62 formed on the surface Wf of the substrate W.

  FIG. 11D is a schematic diagram showing the state of the substrate W during the solid removal step S15. As shown in FIG. 11D, the substrate W is moved relative to the blade 92 in the direction of the arrow AR5 due to the rotation of the substrate W. In this state, the blade 92 is positioned at a predetermined height and comes into contact with the coagulation film 62. Therefore, the blade 92 scrapes off the solid dry auxiliary substance located above the coagulation film 62 in the solid state. Go. As a result, the scraped solid dry auxiliary substance accumulates on the upstream side of the blade 92 in the rotation direction of the substrate W.

  After the blade 92 abuts on the solidified film 62, when the substrate W rotates counterclockwise around the axis A1 by a predetermined number of rotations of one rotation or more, the control unit 13 issues an operation command to the swivel lifting drive unit 14, The arm 93 is turned along the arrow AR4 toward the retracted position P4. As a result, the solid dry auxiliary substance deposited on the upstream side of the blade 92 in the rotation direction of the substrate W is removed to the outside of the substrate W in the radial direction. Thereby, the solidified film 62 is thinned. In the fifth embodiment, the scraping unit 91 corresponds to the “solid removal unit” of the present invention.

  In the fifth embodiment, the film thickness of the solidified film 62 after thinning can be easily adjusted by adjusting the height at which the blade 92 is brought into contact with the solidified film 62.

  After the coagulated film 62 is thinned, the solid dry auxiliary substance adhering to the blade 92 is removed from the blade 92 and collected by a collection mechanism (not shown). The collection mechanism supplies gas or liquid to the scraping surface of the blade 92 (in the fifth embodiment, the surface upstream of the rotation direction of the substrate W of the blade 92), and removes the drying auxiliary material adhering to the scraping surface. A mechanism for removing may be used. At this time, it is preferable to use a liquid in which the drying auxiliary substance is sparingly soluble as the liquid because the drying auxiliary substance and the liquid can be easily separated for the same reason as in the fourth embodiment.

  In addition, the recovery mechanism is configured such that a mechanism such as the nozzle 52 of the suction means 51 of the first embodiment is positioned on the scraping surface of the blade 92 to suck and remove the dry auxiliary substance adhering to the scraping surface. It may be used. In addition, as the recovery mechanism, another blade that slides on the scraping surface of the blade 92 may be provided to scrape and remove the dry auxiliary substance attached to the scraping surface.

  When the melting point of the drying auxiliary substance is lower than the environmental temperature of the chamber 11, a temperature adjusting unit such as a Peltier element is built in the blade 92 or the arm 93 so that the temperature of the blade 92 is higher than the melting point of the drying auxiliary substance. It is good also as a structure made low. Thereby, it is possible to reduce the thickness of the coagulated film 62 while preventing the drying auxiliary substance from melting.

  After the completion of the solid removal step S15, as in the first embodiment, the gas supply means 41 changes the solid dry auxiliary substance into a gas state by sublimation and removes it from the surface Wf of the substrate W.

  Thus, the drying of the surface Wf of the substrate W is completed, and a series of substrate drying processes is completed. After the substrate drying process as described above, the substrate W after the drying process is carried out of the chamber 11 by a substrate carry-in / out mechanism (not shown).

  In the fifth embodiment, the blade 92 is used as an example of the scraping unit 91. However, instead of the blade 92, a brush is used, and the brush is brought into contact with the solidified film to scrape the solidified film. Also good.

<6. Modification>
The first to fifth embodiments of the present invention have been described above. However, these embodiments are merely examples, and the present invention can be implemented in various other forms. Below, other main forms are illustrated.

<6-1. Processing in multiple chambers>
In each of the above embodiments, the cleaning process S11 to the gasification process S16 are performed on the substrate W in one chamber 11. However, the implementation of the present invention is not limited to this, and a chamber may be prepared for each process.

  Specifically, the cleaning process S11 to the solidification process S14 are performed in the first chamber, and after the solidified film is formed on the surface Wf of the substrate W, the substrate W is unloaded from the first chamber, and another second The substrate W on which the solidified film is formed may be carried into the chamber, and the gasification step S16 may be performed in the second chamber.

<6-2. Gasification removal by decompression>
In the first, third, fourth, and fifth embodiments, the gas supply unit 41 is used as the “gasification removing unit” in the gasification step S16. However, the implementation of the present invention is not limited to this, and in the gasification step S16 as in the second embodiment, the decompression means 71 is used to decompress the interior of the chamber 11 by sublimation, thereby sublimating the solid state dry auxiliary substance. You may change to a gaseous state.

<6-3. Solid removal by spin>
In addition to the solid removal step S15 described in the above embodiments, if the adhesion force above the solidified film formed on the surface Wf of the substrate W is particularly weak, after the drying auxiliary liquid is solidified in the solidification step S14 The control unit 13 issues an operation command to the rotation drive unit 151 to increase the rotation speed of the substrate W, so that the solid-state drying auxiliary substance contained in the coagulated film is blown outward in the radial direction of the substrate W by centrifugal force. It is good also as a structure removed. In such a configuration, the substrate holding means 15 corresponds to the “solid removal means” of the present invention.

<6-4. Supplying dry auxiliary substance solution>
In each of the above embodiments, the drying auxiliary liquid tank 27 stores a drying auxiliary liquid containing a molten drying auxiliary substance, and in the drying auxiliary liquid supply step S13, the drying auxiliary liquid is supplied from the nozzle 22 to be solidified. In step S14, a solidified film was formed by solidifying the molten dry auxiliary substance contained in the dry auxiliary liquid.

  However, the embodiment of the present invention is not limited to this, and the drying auxiliary liquid containing the drying auxiliary substance dissolved in the solvent is stored in the drying auxiliary liquid tank 27, and the drying auxiliary liquid supply step S13 supplies the drying auxiliary liquid from the nozzle 22. In the solidification step S14, the solvent contained in the drying auxiliary liquid is removed by evaporation, and the solid dry auxiliary substance is deposited on the surface Wf of the substrate W, so that it is deposited instead of the solidified film. A film may be formed. The solidified film and the deposited film are collectively referred to as “solidified film”.

  In this case, as the drying auxiliary substance, in addition to the substances mentioned in the first embodiment, naphthalene (C10H8), 1,4-dichlorobenzene (molecular formula: C6H4Cl2), tetrachlorodifluoroethane, camphor (molecular formula: C10H16O, system) Name: 1,7,7-trimethylbicyclo [2.2.1] heptan-2-one).

  In the present embodiment, the solvent for the drying auxiliary substance is preferably a liquid that is soluble in the drying auxiliary substance and can be easily dried at room temperature. Examples include IPA, methanol, ethanol, acetone, benzene, carbon tetrachloride, chloroform, hexane, decalin, tetralin, acetic acid, cyclohexanol, ether, or hydrofluoroether (Hydro Fluoro Ether). In addition, when the dry auxiliary substance is water-soluble, DIW can be used in addition to the above solvent.

  In this modification, naphthalene is used as a drying auxiliary substance, and IPA is used as a solvent for the drying auxiliary substance. The drying auxiliary liquid in this modification is a naphthalene solution in which naphthalene is dissolved in IPA.

  The solidification step S14 may be configured such that the gas is supplied to the surface Wf of the substrate W by the gas supply means 41 (FIG. 1 and the like), thereby evaporating the solvent and depositing the drying auxiliary substance. In this case, the gas supply means 41 corresponds to the ““ solidification means ”of the present invention.

<6-5. Oxidation removal of drying aids>
In each of the above embodiments, a substance having sublimation properties is used as the drying auxiliary substance, and in the gasification step S16, the solid state drying auxiliary substance is changed to a gaseous state by sublimation, so that the substrate W is not passed through the liquid state. The substrate W was dried while removing the pattern W from the surface Wf and preventing pattern collapse.

  However, the implementation of the present invention is not limited to this, and a substance that generates a gaseous oxide by oxidation may be used as a dry auxiliary substance. In this case, as the dry auxiliary liquid, a dry auxiliary liquid in which the dry auxiliary substance is in a molten state as in the first embodiment may be used, or a dry auxiliary liquid in a dissolved state as in the above modification may be used. Also good.

Drying auxiliary substances that generate gaseous oxides by oxidation include hexamethylenetetramine (chemical formula: (C ₆ H ₁₂ N _4. Melting point: 280 degrees Celsius. Oxides when oxidized with oxygen or ozone: water vapor, carbon dioxide) And nitrogen oxides, soluble in DIW and IPA), 1,3,5-trioxane (chemical formula: C ₃ H ₆ O _3, melting point: 64 degrees Celsius. Oxides when oxidized with oxygen or ozone: Water vapor and carbon dioxide (soluble in DIW and IPA), ammonium 1-pyrrolidinecarbodithioate (chemical formula: C ₄ H ₈ NCSSNH _4, melting point: 151 ° C. to 153 ° C. when oxidized with oxygen or ozone) Oxides: water vapor, carbon dioxide, nitrogen oxides and sulfur oxides, soluble in DIW and IPA), meta Aldehyde _(Formula: C _{8 H} 16 _{O 4} mp.. C 246 ° oxygen or an oxide upon oxidation with ozone: with soluble to water vapor and carbon dioxide .DIW), or paraffin _{(Formula: C} n H _{2n + 2} (n: 20 to 48) Melting point: 50 degrees Celsius to 52 degrees Celsius. Oxides when oxidized with oxygen or ozone: water vapor and carbon dioxide. Soluble in DIW).

  In addition, when supplying the dry auxiliary substance in a dissolved state, the solvent for the dry auxiliary substance includes DIW and IPA, and a solvent in which the dry auxiliary substance is soluble is selected. In this modification, a hexamethylenetetramine aqueous solution in which hexamethylenetetramine is dissolved in DIW is used as a drying auxiliary liquid. That is, in each of the above-described embodiments, the dry auxiliary liquid tank 27 stores a hexamethylenetetramine aqueous solution.

  When a substance that generates a gaseous oxide by oxidation is used as the drying auxiliary substance, the substrate processing apparatus 1a is further provided with an oxidant supply means for supplying a gaseous oxidant. The oxidant supply means has the same configuration as that of the gas supply means 41 in FIG. 1 and includes a gas tank that stores oxygen gas as a gaseous oxidant instead of the gas tank 47 that stores nitrogen gas. good. As a gaseous oxidant, ozone may be used in addition to oxygen gas.

  In this modification, a hexamethylenetetramine aqueous solution is supplied to the surface Wf of the substrate W in the drying auxiliary liquid supply step S13. Then, as in each of the above-described embodiments, the solidification step S14 and the solid removal step S15 are performed, and a deposited film of the solid dry auxiliary substance (hexamethylenetetramine) is formed on the surface Wf of the substrate W. The

  Moreover, in gasification process S16, an oxidizing agent supply means performs operation | movement similar to the gas supply means 41 of 1st Embodiment, oxygen gas is supplied to a deposited film, oxygen gas and a solid-state drying auxiliary substance Reacts to generate gaseous oxides such as water vapor, carbon dioxide and nitrogen oxides, and the drying auxiliary substances are removed from the surface Wf of the substrate W.

<6-6. Pyrolysis removal of drying aids>
In each of the above embodiments, a substance having sublimation properties is used as the drying auxiliary substance, and in the gasification step S16, the solid state drying auxiliary substance is changed to a gaseous state by sublimation, so that the substrate W is not passed through the liquid state. The substrate W was dried while removing the pattern W from the surface Wf and preventing pattern collapse.

  However, the present invention is not limited to this, and a substance that decomposes into a gaseous product by thermal decomposition may be used as a drying auxiliary substance. In this case, as the dry auxiliary liquid, a dry auxiliary liquid in which the dry auxiliary substance is in a molten state as in the first embodiment may be used, or a dry auxiliary liquid in a dissolved state as in the above modification may be used. Also good. In this modification, a dry auxiliary liquid in a dissolved state is used.

Drying auxiliary substances decomposed into gaseous products by heat include ammonium hydrogen carbonate (chemical formula: NH ₄ HCO _3, thermal decomposition temperature: 58 degrees Celsius. Thermal decomposition products: water vapor, carbon dioxide and ammonia. DIW. Ammonium perchlorate (Chemical formula: NH ₄ ClO ₄₎ Thermal decomposition temperature: about 150 degrees Celsius. Products when pyrolyzed: chlorine, water vapor, nitrogen and oxygen, soluble in DIW Or nitroyl tetrafluoroborate (chemical formula: NO ₂ BF _4, thermal decomposition temperature: 180 degrees Celsius, products upon thermal decomposition: nitroyl fluoride, boron trifluoride), and the like.

  Further, examples of the solvent for the dry auxiliary substance include DIW and IPA, and a solvent in which the dry auxiliary substance is soluble is selected. In this modification, an aqueous ammonium hydrogen carbonate solution in which ammonium hydrogen carbonate is dissolved in DIW is used as the drying auxiliary liquid. That is, in each of the embodiments described above, the aqueous ammonium bicarbonate solution is stored in the drying auxiliary liquid tank 27.

  In the present invention, it is preferable to use a substance having a thermal decomposition temperature of normal temperature or higher and 200 degrees Celsius or lower as the drying auxiliary substance. By selecting a drying auxiliary substance having a thermal decomposition temperature equal to or higher than room temperature, the drying auxiliary liquid can be supplied to the surface Wf of the substrate W without causing thermal decomposition at normal temperature. Further, by selecting a substance having a thermal decomposition temperature of 200 degrees Celsius or lower, thermal decomposition can be caused in the gasification step S16 without setting the chamber 11 to a temperature higher than 200 degrees Celsius. It is not necessary to use a member having high heat resistance as a member constituting the components, and the manufacturing cost of the apparatus can be reduced.

  When a substance that decomposes into a gaseous product by thermal decomposition is used as a drying auxiliary substance, the temperature of the gas stored in the gas storage unit 471 is dried in the temperature adjustment unit 472 of the substrate processing apparatus 1a (see FIG. 5). A configuration is provided in which the temperature is adjusted to be higher than the thermal decomposition temperature of the auxiliary substance. In addition, the piping 45 may be provided with a heating mechanism that raises the gas supplied by the gas supply means 41 to a temperature higher than the thermal decomposition temperature. As the heating mechanism, for example, a resistance heater wound around the pipe 45 is used.

  In the present modification, an aqueous ammonium hydrogen carbonate solution is supplied to the surface Wf of the substrate W in the drying auxiliary liquid supply step S13. Then, as in each of the above-described embodiments, the solidification step S14 and the solid removal step S15 are performed, and a deposited film of the solid dry auxiliary substance (ammonium hydrogen carbonate) is formed on the surface Wf of the substrate W. The

  Moreover, in gasification process S16, the gas supply means 41 performs the operation | movement similar to the gas supply means 41 of 1st Embodiment, gas is supplied to a deposited film, and a solid-state drying auxiliary substance is thermal decomposition temperature. By reaching the above temperature, it undergoes a thermal decomposition reaction and decomposes into gaseous products such as water vapor, carbon dioxide and ammonia, and the drying auxiliary substance is removed from the surface Wf of the substrate W.

<6-7. Other variations>
In the first embodiment, in the solidification step S14, a gas having a temperature lower than the freezing point of the drying auxiliary substance is supplied by the gas supply unit 41 to form the solidified film 62 on the surface Wf. However, the implementation of the present invention is not limited to this.

  Specifically, in place of the spin base 152 and the chuck pin 153 of FIG. 1, a spin chuck that directly contacts the central portion of the back surface Wb of the substrate W and sucks and holds the substrate W is provided. For example, the substrate W may be cooled from the back surface Wb by cooling with cold water piping or using a Peltier element, and the drying auxiliary liquid 61 on the front surface Wf may be cooled to a temperature lower than the freezing point.

  In addition, a liquid or gas having a temperature lower than the freezing point of the drying auxiliary substance from the back surface Wb side of the substrate W to the substrate W is provided in the central portion of the spin base 152 of FIG. In which the substrate W is cooled from the back surface Wb by supplying a refrigerant (for example, nitrogen gas at 7 degrees Celsius or cold water at 7 degrees Celsius), and the drying auxiliary liquid 61 on the surface Wf is cooled to a temperature lower than the freezing point. It is good.

  A plurality of components included in each embodiment and each modification of the present invention described above are not all essential, and are described in the present specification to solve part or all of the above-described problems. In order to achieve part or all of the effects obtained, some of the constituent elements of the plurality of constituent elements may be changed, deleted, replaced with other new constituent elements, or part of the limited content may be deleted as appropriate. Is possible. In addition, in order to solve part or all of the above-described problems or to achieve part or all of the effects described in the present specification, each of the embodiments and modifications of the present invention described above is provided. Part or all of the technical features included in the above are combined with part or all of the technical features included in the other embodiments or other modifications of the present invention described above to form independent embodiments of the present invention. It is also possible.

  The invention of the present application can be applied to a drying technique for removing liquid adhering to the surface of the substrate and a substrate processing technique for treating the surface of the substrate using the drying technique.

DESCRIPTION OF SYMBOLS 1a, 1b, 1c Substrate processing apparatus 11 Chamber 12 Spattering prevention cup 13 Control unit 14 Turning raising / lowering drive part 15 Substrate holding means 21 Drying auxiliary liquid supply means 31 IPA supply means 41 Gas supply means 51 Suction means 61 Drying auxiliary liquid 62 Coagulation film 71 Depressurization means 81 DIW supply means 91 Scraping means S11 Cleaning process S12 Rinsing process S13 Drying auxiliary liquid supply process S14 Solidification process S15 Solid removal process S16 Gasification process W Substrate

Claims (10)

A drying auxiliary liquid supply means for supplying a drying auxiliary liquid containing a drying auxiliary substance to the surface of the substrate to which the treatment liquid is attached;
Solidification means for changing the dry auxiliary substance contained in the dry auxiliary liquid into a solid state by precipitation or solidification on the surface of the substrate;
Solid removal means for removing the dry auxiliary substance in the solid state on the surface of the substrate from the surface of the substrate while maintaining the solid state;
Gasifying means for removing the drying auxiliary substance in a solid state on the surface of the substrate from the substrate by sublimation, thermal decomposition or oxidation to change it into a gaseous state;
A substrate processing apparatus comprising: The substrate processing apparatus according to claim 1,
The solid removing unit sprays a fluid onto the surface of the substrate to remove the drying auxiliary substance in the solid state from the surface of the substrate.
A substrate processing apparatus. The substrate processing apparatus according to claim 2,
The solid removing means sprays a gas having a temperature lower than the melting point of the drying auxiliary substance on the surface of the substrate;
A substrate processing apparatus. The substrate processing apparatus according to claim 1,
The solid removal means is a suction means for sucking the drying auxiliary substance in a solid state on the surface of the substrate.
A substrate processing apparatus. The substrate processing apparatus according to claim 1,
The solid removal means is a scraping means for scraping off the drying auxiliary substance in a solid state on the surface of the substrate.
A substrate processing apparatus. A substrate processing apparatus according to any one of claims 1 to 5, wherein
The drying auxiliary liquid supply means supplies the drying auxiliary liquid containing the melted drying auxiliary substance to the surface of the substrate,
The solidifying means solidifies the melted dry auxiliary substance on the surface of the substrate;
A substrate processing apparatus. A substrate processing apparatus according to any one of claims 1 to 5, wherein
The dry auxiliary liquid supply means supplies the dry auxiliary liquid containing a solution in which the dry auxiliary substance is dissolved in a solvent to the surface of the substrate,
The solidification means removes the solvent contained in the drying auxiliary liquid and deposits the drying auxiliary substance on the surface of the substrate;
A substrate processing apparatus. A substrate processing apparatus according to any one of claims 1 to 7,
The gasifying means sublimates the solid dry auxiliary substance on the surface of the substrate and removes it from the substrate.
A substrate processing apparatus. The substrate processing apparatus according to claim 8, comprising:
The drying aid is pure water, tertiary butanol, or 1,1,2,2,3,3,4-heptafluorocyclopentane.
A substrate processing apparatus. A drying auxiliary liquid supplying step of supplying a drying auxiliary liquid containing a drying auxiliary substance to the surface of the substrate to which the treatment liquid is attached;
A solidification step of changing the dry auxiliary substance contained in the dry auxiliary liquid into a solid state by precipitation or solidification on the surface of the substrate;
A solid removal step of removing the drying auxiliary substance in a solid state on the surface of the substrate from the surface of the substrate while maintaining the solid state;
After performing the solid removal step, the drying auxiliary substance in the solid state on the surface of the substrate is sublimated, pyrolyzed or oxidized to change to a gaseous state, and a gasification step for removing from the substrate,
A substrate processing method comprising:

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