JP5202865B2 - Substrate processing method and substrate processing apparatus - Google Patents

Description

The present invention relates to a substrate processing method and a substrate processing apparatus for processing a substrate using a processing liquid . Examples of substrates to be processed include semiconductor wafers, liquid crystal display substrates, plasma display substrates, FED (Field Emission Display) substrates, optical disk substrates, magnetic disk substrates, magneto-optical disk substrates, photo A mask substrate is included.

A substrate processing apparatus used in a manufacturing process of a semiconductor device or the like includes, for example, a spin chuck that rotates while holding a single substrate substantially horizontally, and a processing liquid (chemical solution or rinsing liquid) applied to the substrate held by the spin chuck. And a treatment liquid nozzle to be supplied. A processing liquid in a certain state is discharged from the processing liquid nozzle, and the processing liquid reaches the surface of the substrate. That is, when the chemical liquid is discharged from the processing liquid nozzle, the process parameters such as the temperature, concentration, composition, flow rate, and pressure of the chemical liquid are controlled to constant target values. Also, when a rinse liquid (for example, pure water (deionized pure water)) is discharged from the treatment liquid nozzle, process parameters such as temperature, flow rate and pressure of the rinse liquid are kept constant.
Japanese Patent Laid-Open No. 4-171931

However, if the state of the processing liquid is kept constant, the state on the substrate surface becomes constant, and it is difficult to cause a significant change on the substrate surface.
For example, in a process of supplying an ammonia-hydrogen peroxide mixture (APM) to the substrate to remove particles on the substrate surface, the state of the ammonia-hydrogen peroxide mixture is constant. If there is, it is difficult to exert large particle removal performance.

In addition, in the process of supplying a hydrochloric acid / hydrogen peroxide mixture (HPM) to the substrate to remove metal contaminants on the substrate surface, the state of the hydrochloric acid / hydrogen peroxide mixture is constant. If there is, large metal decontamination performance cannot be expected.
SUMMARY OF THE INVENTION An object of the present invention is to provide a substrate processing method and a substrate processing apparatus capable of causing a remarkable change on the substrate surface during substrate processing with a processing liquid , thereby improving processing efficiency. That is.

The invention of claim 1, wherein for achieving the above object, a treatment liquid supply step of supply supplying the treatment liquid to perform the processing on the substrate to the substrate, during the treatment liquid supply process, is supplied to the substrate The substrate processing method includes a fluctuation applying step for applying fluctuation capable of causing a change in the state of the substrate surface without inhibiting target substrate processing with respect to the process parameters relating to the processing liquid .
“Fluctuation” generally refers to “a phenomenon that is macroscopically constant but microscopically fluctuates around an average value” (Kojien 5th edition), and the process parameter “fluctuation” By means that the process parameter exhibits a variation in a sufficiently short time interval for its macroscopic behavior (eg constant, gradual increase or decrease). The “sufficiently short time interval” in this case is a time interval that can be sufficiently ignored with respect to a macroscopic time change of the process parameter, and is a short time interval that does not hinder the target substrate processing.

“Process parameters relating to the processing liquid ” refers to parameters affecting the substrate processing among parameters that define the state of the processing liquid .
According to the first aspect of the present invention, when the processing liquid is supplied to the substrate, the process parameter related to the processing liquid is given fluctuation. As a result, fluctuation occurs in the state of the processing liquid supplied to the substrate, and accordingly, remarkable fluctuation (fluctuation) can be given to the state of the substrate surface. As a result, the processing efficiency with the processing liquid can be improved. In this case, the “state of the substrate surface” includes not only the state of the surface of the substrate itself but also the state of particles present on the substrate surface, metal contamination, and the like.

When imparting fluctuations to the process parameter, the process parameter may be continuously changed or may be changed stepwise (pulse-like). By changing the process parameters stepwise, more significant changes can be made on the substrate surface.
A second aspect of the present invention is the substrate processing method according to the first aspect, wherein the process parameter includes a parameter relating to an activity of the processing liquid . According to this invention, since the activity of the processing liquid is fluctuated, a remarkable change can be caused in the state of the substrate surface, and the processing efficiency by the processing liquid can be increased.

Preferably, the parameter relating to the activity includes at least one of a temperature and a concentration of the treatment liquid . Thereby, since a microscopic change can be given to temperature or a density | concentration, a remarkable change can be produced in the state of a substrate surface, and the processing efficiency by a process liquid can be improved reliably.
Invention of claim 4, wherein the processing solution is a mixed solution prepared by mixing a plurality of kinds of liquid, the parameters related to the activity includes the degree of mixing of the mixed liquid according to claim 2 or 3 It is a substrate processing method of description. According to the present invention, fluctuation is generated in the activity by giving fluctuation to the mixing degree of the mixed solution . Thereby, fluctuations can be imparted to the state of the substrate surface, and the efficiency of substrate processing with the mixed liquid can be increased.

Examples of the mixed solution include a sulfuric acid / hydrogen peroxide mixture (SPM) prepared by mixing sulfuric acid and hydrogen peroxide solution. A mixture of sulfuric acid and hydrogen peroxide produces a strong oxidizing power by mixing sulfuric acid and hydrogen peroxide, and the oxidizing power is further strengthened by reaction heat. Used as a resist stripper for stripping. Since the strength of the oxidizing power of the sulfuric acid / hydrogen peroxide mixture varies depending on the degree of mixing, the degree of activity can be fluctuated by fluctuating the degree of mixing.

A fifth aspect of the present invention is the substrate processing method according to any one of the first to fourth aspects, wherein the process parameter includes a parameter related to a physical force of the processing liquid . According to the present invention, fluctuations are imparted to the physical force of the processing liquid , so that a remarkable change is caused in the state of the substrate surface, and the substrate can be processed with high efficiency.
Preferably, the parameter relating to the physical force includes at least one of a temperature, a flow rate, and a pressure of the processing liquid . When fluctuation is applied to the temperature of the processing solution , the substrate is expanded / contracted, so that the state of the substrate surface can be significantly changed. Further, when fluctuation is applied to the flow rate or pressure, a change occurs in the impact force when the liquid collides with the substrate surface. In this way, significant changes can be made in the state of the substrate surface.

Invention according to claim 7, wherein the processing solution is a mixed solution prepared by mixing a plurality of kinds of liquid, the process parameters, including the composition ratio of the mixed solution, any of claims 1 to 6 The substrate processing method according to claim 1. According to this invention, the fluctuation of the composition ratio of the mixed liquid significantly changes the state of the substrate surface. Thereby, the substrate processing efficiency by the processing liquid can be improved.

  The invention according to claim 8 is the substrate processing method according to any one of claims 1 to 6, wherein the fluctuation applying step includes a step of repeatedly increasing and decreasing a process parameter. By repeating the increase / decrease of the process parameter in this way, fluctuations are given to the process parameter. The increase width and decrease width of the process parameter may or may not be equal. That is, the process parameter may be varied within a certain amplitude range so that the macroscopic behavior of the process parameter may be constant, or the process parameter is caused to undergo a macroscopic time change, and the process parameter is increased gradually or macroscopically. You may make it reduce gradually. In other words, the time average value of the process parameter (the average value over a time sufficient for the fluctuation of the process parameter) may be constant, or may be gradually increased or gradually decreased.

  The invention according to claim 9 is the substrate processing method according to any one of claims 1 to 6, wherein the fluctuation applying step includes a step of periodically increasing and decreasing process parameters. According to the present invention, periodic fluctuations can be imparted to the process parameters. In this case, the fluctuation cycle does not hinder the intended substrate processing, and can cause a change (fluctuation) in the state of the substrate surface (the state of the substrate, the state of foreign matter on the substrate surface, etc.). It may be determined.

The invention of claim 10 wherein the processing solution supply means for supply supplying the treatment liquid to perform the processing on the substrate to the substrate (2～5,9,61～64,71～74), the treatment liquid supply means Fluctuation imparting means (7, 30, 33, 41) that imparts fluctuation that can cause a change in the state of the substrate surface without impairing the target substrate processing with respect to the process parameters relating to the processing liquid to be supplied. 44, 51-53, 55, 78, 79, 101-104). The alphanumeric characters in parentheses indicate corresponding components in the embodiments described later.

With this configuration, when the processing liquid is supplied to the substrate, fluctuations are given to the process parameters regarding the processing liquid . As a result, fluctuation occurs in the state of the processing liquid supplied to the substrate, and accordingly, remarkable fluctuation (fluctuation) can be given to the state of the substrate surface. As a result, the processing efficiency with the processing liquid can be improved.
Regarding the invention of the substrate processing apparatus, the same modifications as those of the invention of the substrate processing method are possible.

  The treatment for the substrate may be, for example, an etching (cleaning) treatment for removing unnecessary substances such as particles (particles) and various metal contaminants from the surface of the substrate, or an oxidation treatment for forming an oxide film on the surface of the substrate. It may be. Or the resist peeling process which removes the resist of the surface of a board | substrate may be sufficient, and the polymer removal process which removes the resist residue (polymer) of the surface of a board | substrate may be sufficient.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
FIG. 1 is a diagram showing a simplified configuration of a substrate processing apparatus according to an embodiment of the present invention. This substrate processing apparatus is a single wafer processing apparatus that processes substrates W such as semiconductor wafers one by one. The substrate processing apparatus includes a spin chuck 1 that rotates while holding the substrate W substantially horizontally.

  The spin chuck 1 has a spin shaft 11 extending in the vertical direction, a spin base 12 attached to the upper end of the spin shaft 11, and a plurality of clamping members 13 disposed on the peripheral edge of the spin base 12. doing. The plurality of clamping members 13 are arranged on a circumference corresponding to the outer shape of the substrate W, and hold the substrate W in a substantially horizontal posture by clamping the peripheral surface of the substrate W at a plurality of different positions. be able to. In addition, a rotational driving mechanism 14 including a driving source such as a motor is coupled to the spin shaft 11, and a driving force is applied from the rotational driving mechanism 14 to the spin shaft 11 while the substrate W is held by a plurality of clamping members 13. By inputting, the substrate W can be rotated around the central axis of the spin shaft 11 in a substantially horizontal posture.

Note that the spin chuck 1 is not limited to such a configuration, and for example, the lower surface of the substrate W is vacuum-sucked to hold the substrate W in a substantially horizontal posture, and in that state, around the vertical axis. A vacuum chucking type (vacuum chuck) that can rotate the held substrate W by rotation may be employed.
A processing liquid nozzle 2 for supplying a processing liquid to the surface (upper surface) of the substrate W held on the spin chuck 1 is provided above the spin chuck 1. For example, the processing liquid nozzle 2 is attached to the tip of an arm (not shown) extending in a substantially horizontal direction above the spin chuck 1 with a discharge port for discharging the processing liquid facing downward. The landing point of the processing liquid from the processing liquid nozzle 2 on the surface of the substrate W held by the spin chuck 1 by swinging the arm in a substantially horizontal plane (reciprocating swivel within a predetermined angle range). Can be scanned (moved).

  A chemical liquid or a rinsing liquid is supplied to the processing liquid nozzle 2 from the processing liquid supply path 3. In this embodiment, the rinsing liquid is pure water (DIW: deionized pure water; normal temperature) or warm pure water (HDIW: deionized hot pure water; higher than DIW). In this embodiment, the chemical solution is a mixed solution of a chemical solution stock solution and a rinse solution (normal temperature pure water or warm pure water).

  The processing liquid supply path 3 has one end coupled to the processing liquid nozzle 2 and the other end coupled to the mixing valve 4. The mixing valve 4 includes a mixing unit 40 for mixing the processing liquid, and chemical solution introduction valves 41, 42, 43, 44 coupled to the mixing unit 40. Further, the pure water introduction path 5 is coupled to the mixing unit 40, and pure water (DIW or HDIW) is supplied through the pure water introduction path 5. In a state where pure water is introduced from the pure water introduction path 5 into the mixing unit 40, the chemical solution stock solution and the pure water are mixed by opening any one or two or more of the chemical solution introduction valves 41 to 44. The chemical solution to be supplied to the substrate W can be prepared. Thus, since the chemical liquid is prepared immediately before discharge from the processing liquid nozzle 2, it is possible to suppress the deterioration of the medicinal component and to effectively treat the chemical liquid as compared with the configuration in which the prepared chemical liquid is stored in the tank. Can be done automatically.

The chemical solution introduction valves 61, 62, 63, and 64 are coupled to the chemical solution introduction valves 41, 42, 43, and 44, respectively. A chemical solution stock solution is supplied to these chemical solution introduction paths 61, 62, 63, and 64 from chemical solution supply sources 71, 72, 73, and 74, respectively. The “chemical solution stock” as used herein means a chemical solution before being diluted with pure water.
For example, the chemical solution supply source 71 supplies hydrogen peroxide water (H ₂ O ₂ ) to the chemical solution introduction channel 61, the chemical solution supply source 72 supplies hydrochloric acid (HCl) to the chemical solution introduction channel 62, and the chemical solution supply source 73 supplies ammonia. Water (NH ₄ OH) is supplied to the chemical solution introduction path 63, and the chemical solution supply source 74 supplies hydrofluoric acid (HF) to the chemical solution introduction path 64.

  The chemical solution introduction paths 61, 62, 63, 64 have filters 81, 82, 83, 84, flow meters 91, 92, 93, 94, and flow rate adjustment valves 101, respectively, in order from the chemical solution supply sources 71 to 74 side. 102, 103, and 104 are interposed. In addition, pressure gauges 86, 87, 88, 89 are arranged between the flow meters 91, 92, 93, 94 and the flow rate adjusting valves 101, 102, 103, 104, respectively. The filters 81 to 84 remove foreign substances in the supplied chemical solution stock solution. The flow meters 91-94 measure the flow rate of the chemical solution stock passing through the chemical solution introduction paths 61-64. The flow rate adjusting valves 101 to 104 variably set the flow rate of the chemical solution passing through the chemical solution introduction paths 61 to 64. The pressure gauges 86, 87, 88 and 89 measure the pressure of the chemical solution stock solution in the chemical solution introduction paths 61 to 64.

  When the chemical liquid used for processing the substrate W is a hydrochloric acid hydrogen peroxide water mixed liquid (HPM), in the mixing valve 4, the hydrogen peroxide solution introduced through the chemical liquid introduction valve 41 and the chemical liquid introduction valve 42 are used. Hydrochloric acid introduced via the pure water introduced from the pure water introduction path 5 is mixed. Further, when the chemical liquid used for processing the substrate W is an ammonia hydrogen peroxide water mixed liquid (APM), the mixing valve 4 introduces the hydrogen peroxide water introduced through the chemical liquid introduction valve 41 and the chemical liquid introduction. Ammonia water introduced through the valve 43 and pure water introduced from the pure water introduction path 5 are mixed. Further, when the chemical solution used for processing the substrate W is dilute hydrofluoric acid (DHF), the mixing valve 4 introduces the hydrofluoric acid introduced through the chemical solution introduction valve 44 and the pure water introduction path 5. Pure water is mixed.

  Thus, for example, metal contamination removal treatment using a hydrochloric acid hydrogen peroxide solution mixture, particle removal treatment using an ammonia hydrogen peroxide solution mixture, and natural oxide film removal treatment using dilute hydrofluoric acid can be performed. it can. In this case, the concentration of the chemical solution and the mixed composition can be adjusted by controlling the flow rate adjusting valves 101, 102, 103, 104. Moreover, the temperature of a chemical | medical solution can be changed by switching normal temperature pure water and warm pure water higher than normal temperature.

The chemical solution supply source 71 includes a chemical solution tank 76 that stores the chemical solution stock solution 75 and a nitrogen gas supply path 77 that is connected to the chemical solution tank 76. One end of the chemical solution introduction path 61 is immersed in a chemical solution stock solution 75 stored in the chemical solution tank 76. The chemical liquid tank 76 is formed of a sealed container. By introducing nitrogen gas (N ₂ ) from the nitrogen gas supply path 77 into the chemical liquid tank 76, the pressure in the chemical liquid tank 76 is increased, and the chemical liquid stock solution 75 is It is sent out to the chemical solution introduction path 61. The nitrogen gas supply path 77 is provided with a regulator 78 for adjusting the nitrogen gas pressure and a nitrogen gas valve 79 for opening and closing the nitrogen gas supply path 77.

Since the configuration of the chemical liquid supply sources 72 to 74 is substantially the same as that of the chemical liquid supply source 71, illustration and detailed description thereof are omitted.
The pure water introduction path 5 is selectively supplied with pure water (DIW) or hot pure water (HDIW) at room temperature via a pure water supply source valve 51 or a warm pure water supply source valve 52. Further, the pure water introduction path 5 includes a regulator 53 for adjusting the flow pressure of pure water supplied to the pure water introduction path 5 in order from the upstream side in the flow direction of the pure water, and the pure water introduction path 5. A flow meter 54 for measuring the flow rate of pure water flowing through the water and a pure water valve 55 for opening and closing a flow path between the flow meter 54 and the mixing valve 4 are interposed. Further, a pressure gauge 56 for measuring the pressure of pure water in the pure water introduction path 5 is disposed between the flow meter 54 and the pure water valve 55.

  FIG. 2 is a block diagram showing an electrical configuration of the substrate processing apparatus. The substrate processing apparatus includes a control device 7 composed of, for example, a microcomputer. The control device 7 includes a rotation drive mechanism 14, a chemical solution introduction valve 41 to 44, a pure water supply source valve 51, a warm pure water supply source valve 52, regulators 53 and 78, flow meters 54 and 91 to 94, a pure water valve 55, a pressure A total of 56, 86 to 89, a nitrogen gas valve 79, and flow rate adjusting valves 101 to 104 are connected. The control device 7 controls the operations of the rotary drive mechanism 14 and the regulators 53 and 78 according to a predetermined program for processing the substrate W, and the pressure gauges 56 and 86 to 89 and the flow meters 54 and 91 to 94. And the opening and closing of the flow rate adjusting valves 101 to 104 are controlled by controlling the opening and closing of the nitrogen gas valve 79, the chemical solution introduction valves 41 to 44, the pure water supply source valve 51, the warm pure water supply source valve 52 and the pure water valve 55. Control the degree.

  FIG. 3 is a flowchart for explaining an example of the processing steps for one substrate W. When the substrate W to be processed is loaded into the spin chuck 1 (step S1), the control device 7 drives the rotation drive mechanism 14 to rotate the substrate W at a predetermined liquid processing speed (step S2). At this time, the chemical solution introduction valves 41 to 44, the pure water supply source valve 51, the warm pure water supply source valve 52, and the pure water valve 55 are all controlled to be closed.

When the rotation speed of the substrate W reaches the liquid processing speed, the control device 7 controls the pure water supply source valve 51, the warm pure water supply source valve 52, the pure water valve 55, the hydrogen peroxide solution chemical introduction valve 41, and the ammonia water. By controlling the chemical solution introduction valve 43 and the like, the ammonia hydrogen peroxide solution mixture (APM) is discharged from the processing solution nozzle 2 onto the surface of the substrate W (step S3).
More specifically, the pure water supply source valve 51 or the warm pure water supply source valve 52 is opened, and further, the pure water valve 55 is opened, whereby normal temperature pure water or warm pure water is introduced into the mixing unit 40 of the mixing valve 4. Is done. On the other hand, when the chemical solution introduction valves 41 and 43 are opened, the hydrogen peroxide solution and the ammonia solution from the chemical solution supply sources 71 and 73 are introduced into the mixing unit 40 of the mixing valve 4. Thereby, the mixing ratio (composition ratio) corresponding to the ratio (flow rate ratio) of the hydrogen peroxide water flow rate through the chemical solution introduction channel 61, the ammonia water flow rate through the chemical solution introduction channel 63, and the pure water flow rate through the pure water introduction channel 5. ), A hydrogen peroxide solution, an ammonia solution and a pure water are mixed to prepare an ammonia hydrogen peroxide solution mixture. The prepared ammonia hydrogen peroxide solution mixture is sent to the treatment liquid nozzle 2 via the treatment liquid supply path 3 and discharged toward the surface of the rotating substrate W. Thus, the ammonia hydrogen peroxide solution mixture is discharged onto the surface of the substrate W, whereby particles on the surface of the substrate W are removed.

During the period in which the ammonia hydrogen peroxide solution mixture is supplied to the substrate W, an APM fluctuation applying step for applying fluctuation to the ammonia hydrogen peroxide solution treatment condition is performed (step S4). Details of the APM fluctuation application step will be described later.
After the treatment with the ammonia hydrogen peroxide solution mixture for a predetermined time, the control device 7 closes the chemical solution introduction valves 41 and 43. Thereby, only the pure water from the pure water introduction path 5 is supplied to the mixing valve 4. In this way, pure water is supplied from the processing liquid nozzle 2 toward the surface of the substrate W, and a first intermediate rinsing step for washing away the ammonia hydrogen peroxide solution mixed solution on the substrate W is performed (step S5).

  After the first intermediate rinsing process is performed for a predetermined time, the control device 7 opens the chemical solution introduction valve 41 for hydrogen peroxide solution and the chemical solution introduction valve 42 for hydrochloric acid. As a result, the hydrogen peroxide solution and hydrochloric acid from the chemical liquid supply sources 71 and 72 are introduced into the mixing unit 40 of the mixing valve 4. Thereby, the mixing ratio (composition ratio) corresponding to the ratio (flow rate ratio) of the hydrogen peroxide flow rate through the chemical solution introduction channel 61, the hydrochloric acid flow rate through the chemical solution introduction channel 62, and the pure water flow rate through the pure water introduction channel 5. The hydrogen peroxide solution, hydrochloric acid and pure water are mixed to prepare a hydrochloric acid hydrogen peroxide solution mixture (HPM). The prepared hydrochloric acid / hydrogen peroxide solution mixture is sent to the processing liquid nozzle 2 through the processing liquid supply path 3 and discharged toward the surface of the rotating substrate W (step S6). In this way, the metal-contaminant on the surface of the substrate W is removed by discharging the hydrochloric acid / hydrogen peroxide solution mixture onto the surface of the substrate W.

During the period in which the hydrochloric acid / hydrogen peroxide solution mixture is supplied to the substrate W, an HPM fluctuation applying step for applying fluctuation to the hydrochloric acid / hydrogen peroxide solution treatment condition is performed (step S7). Details of this HPM fluctuation application step will be described later.
After the treatment with the hydrochloric acid / hydrogen peroxide mixture is performed for a predetermined time, the control device 7 closes the chemical solution introduction valves 41 and 42. Thereby, only the pure water from the pure water introduction path 5 is supplied to the mixing valve 4. In this way, pure water is supplied from the processing liquid nozzle 2 toward the surface of the substrate W, and a second intermediate rinsing step for washing away the hydrochloric acid / hydrogen peroxide mixture on the substrate W is performed (step S8).

  After the second intermediate rinsing step is performed for a predetermined time, the control device 7 opens the chemical solution introduction valve 44 for hydrofluoric acid. Thereby, hydrofluoric acid from the chemical solution supply source 74 is introduced into the mixing unit 40 of the mixing valve 4. Thereby, hydrofluoric acid and pure water are mixed at a mixing ratio (composition ratio) corresponding to the ratio (flow ratio) of the flow rate of hydrofluoric acid passing through the chemical solution introduction path 64 and the flow rate of pure water passing through the pure water introduction path 5. The diluted hydrofluoric acid is prepared, and the prepared diluted hydrofluoric acid is sent to the processing liquid nozzle 2 through the processing liquid supply path 3 and discharged toward the surface of the rotating substrate W (step S9). . In this way, the dilute hydrofluoric acid is discharged onto the surface of the substrate W, whereby the natural oxide film on the surface of the substrate W is removed, and foreign matters (particles, etc.) on the surface of the natural oxide film are also removed simultaneously.

During the period in which dilute hydrofluoric acid is supplied to the substrate W, a hydrofluoric acid fluctuation imparting step for imparting fluctuation to the dilute hydrofluoric acid treatment conditions is performed (step S10). Details of the hydrofluoric acid fluctuation imparting step will be described later.
After the treatment with dilute hydrofluoric acid is performed for a predetermined time, the control device 7 closes the chemical solution introduction valve 41. Thus, the treatment with dilute hydrofluoric acid is completed, and only the pure water from the pure water introduction path 5 is supplied to the mixing valve 4. In this way, pure water is supplied from the processing liquid nozzle 2 toward the surface of the substrate W, and a final rinsing step is performed to wash away the diluted hydrofluoric acid on the substrate W (step S11).

During the final rinsing process, a rinsing fluctuation applying process for applying fluctuations to the rinsing process conditions is performed (step S12). Details of the rinse fluctuation application step will be described later.
When the final rinsing process while applying fluctuation is performed for a predetermined time, the control device 7 closes the pure water valve 55 and stops the discharge of pure water from the processing liquid nozzle 2. Further, the control device 7 controls the rotation drive mechanism 14 to accelerate the rotation speed of the substrate W by the spin chuck 1 to a predetermined drying speed (for example, 3000 rpm). As a result, a drying process is performed in which the pure water adhering to the surface of the substrate W after cleaning is spun off by a centrifugal force and dried (step S13).

When this drying process is completed, the rotation of the substrate W by the spin chuck 1 is stopped, and the processed substrate W is unloaded from the spin chuck 1 by a transfer robot (not shown) (step S14).
When processing a plurality of substrates W, the above processing is repeated by the number of substrates W to be processed.

Next, the APM fluctuation application process (step S4) will be described.
The APM fluctuation imparting step includes at least one of the following steps A1 to A7. Of course, you may perform an APM fluctuation provision process by combining two or more processes of these, and performing them sequentially or simultaneously.
A1: Hydrogen peroxide water on / off process A2: Ammonia water on / off process A3: Hydrogen peroxide water flow rate changing process A4: Ammonia water flow rate changing process A5: Pure water on / off process A6: Pure water temperature switching process A7 : Pure water flow rate changing step The hydrogen peroxide solution on / off step A1 is a state in which the hydrogen peroxide solution is supplied to the mixing unit 40 of the mixing valve 4 by opening / closing the hydrogen peroxide solution chemical introduction valve 41. And a state of not being supplied. For example, the opening / closing cycle of the chemical solution introduction valve 41 may be about 4 seconds (for example, it is opened for 2 seconds and then closed for 2 seconds). By the hydrogen peroxide solution on / off step A1, hydrogen peroxide solution is intermittently supplied to the mixing unit 40, and therefore, the hydrogen peroxide solution is also intermittently supplied to the surface of the substrate W. As a result, the state of the surface of the substrate W changes in a short cycle, so that a significant change (fluctuation) can be given to the state of the surface of the substrate W.

  The ammonia water on / off step A2 is a step of switching between a state in which ammonia water is supplied to the mixing unit 40 of the mixing valve 4 and a state in which it is not supplied by controlling opening and closing of the chemical solution introduction valve 43 for ammonia water. For example, the opening / closing cycle of the chemical solution introduction valve 43 may be about 4 seconds (for example, it is opened for 2 seconds and then closed for 2 seconds). By this ammonia water on / off step A2, ammonia water is intermittently supplied to the mixing unit 40, and therefore, ammonia water is intermittently supplied to the surface of the substrate W. As a result, the state of the surface of the substrate W changes in a short cycle, so that a remarkable change (fluctuation) can be given to the state of the surface of the substrate W.

  The hydrogen peroxide flow rate changing step A3 is a step of increasing or decreasing the flow rate of the hydrogen peroxide solution introduced into the mixing portion 40 of the mixing valve 4 by increasing or decreasing the opening degree of the hydrogen peroxide flow rate adjusting valve 101. is there. For example, the opening degree of the flow rate adjustment valve 101 may be increased or decreased with a period of about 5 seconds. The opening degree of the flow rate adjusting valve 101 may be increased or decreased continuously or may be increased or decreased stepwise. By the hydrogen peroxide solution flow rate changing step A3, the supply flow rate of the hydrogen peroxide solution to the surface of the substrate W is changed in a short cycle. Thereby, a remarkable change (fluctuation) can be given to the state of the substrate W surface. That is, the concentration of hydrogen peroxide solution in the processing liquid supplied to the surface of the substrate W (in other words, the composition of the processing liquid) can be increased or decreased in a short cycle.

  The ammonia water flow rate changing step A4 is a step of increasing or decreasing the flow rate of the ammonia water introduced into the mixing unit 40 of the mixing valve 4 by increasing or decreasing the opening degree of the ammonia water flow rate adjusting valve 103. For example, the opening degree of the flow rate adjustment valve 103 may be increased or decreased with a period of about 5 seconds. The opening degree of the flow rate adjusting valve 103 may be increased or decreased continuously or in steps. By the ammonia water flow rate changing step A4, the supply flow rate of the ammonia water to the surface of the substrate W is changed in a short cycle. Thereby, a remarkable change (fluctuation) can be given to the state of the substrate W surface. That is, the ammonia concentration (in other words, the composition of the processing liquid) in the processing liquid supplied to the surface of the substrate W can be increased or decreased in a short cycle.

  The pure water on / off step A5 is a step of switching between a state in which pure water is supplied to the mixing unit 40 of the mixing valve 4 and a state in which the pure water is not supplied by controlling the opening and closing of the pure water valve 55. For example, the cycle of opening and closing the pure water valve 55 is preferably about 4 seconds (for example, it is opened for 2 seconds and then closed for 2 seconds). Thereby, since the supply of pure water to the surface of the substrate W becomes intermittent, the state of the surface of the substrate W can be changed with time in a short cycle.

  In the pure water temperature switching step A6, the warm pure water supply source valve 52 is closed, the pure water supply source valve 51 is opened and normal temperature pure water is supplied to the pure water introduction path 5, and the pure water supply source valve 51 is closed. In this step, the warm pure water supply source valve 52 is opened to switch the state of supplying warm pure water having a temperature higher than room temperature to the pure water introduction path 5. The switching cycle between the room temperature pure water and the temperature pure water may be, for example, about 10 seconds (for example, supplying room temperature pure water for 5 seconds and then supplying warm pure water for 5 seconds). Thereby, since the temperature of the processing liquid supplied to the surface of the substrate W changes with time in a short cycle, the activity of the processing liquid can be fluctuated. In addition, thermal expansion and thermal contraction of the substrate W occur as the temperature of the processing liquid changes. In this way, fluctuations can be imparted to the state of the substrate W surface.

  The pure water flow rate changing step A7 is a step of increasing or decreasing the flow rate of pure water (room temperature pure water or warm pure water) flowing through the pure water introduction path 5 by changing the adjustment pressure of the regulator 53. The increase / decrease of the pure water flow rate may be performed, for example, at a cycle of about 5 seconds. Thereby, since the pure water flow rate increases and decreases, the concentration (in other words, composition ratio) of the treatment liquid can be increased and decreased in a short cycle. Thus, a remarkable change can be given to the surface state of the substrate W. The flow rate of pure water may be increased or decreased continuously, or may be increased or decreased in steps.

  For example, in order to give fluctuation to the concentration of the ammonia hydrogen peroxide solution mixture, the hydrogen peroxide solution flow rate changing step A3 and the ammonia water flow rate changing step A4 may be performed in parallel. In this case, the hydrogen peroxide water flow rate and the ammonia water flow rate are increased or decreased in synchronization. That is, when the hydrogen peroxide water flow rate is increased, the ammonia water flow rate is also increased, and when the hydrogen peroxide water flow rate is decreased, the ammonia water flow rate is also decreased. Thereby, the density | concentration of ammonia hydrogen peroxide solution liquid mixture can be increased / decreased. It is not necessary to increase or decrease the concentration within a certain amplitude range. For example, the ammonia hydrogen peroxide solution mixture gradually shifts to the high concentration side or the low concentration side while increasing or decreasing the concentration. The concentration can also be changed.

As described above, the application of fluctuation to the concentration of the ammonia hydrogen peroxide solution mixture can also be performed by the pure water flow rate changing step A7.
In order to give fluctuation to the composition ratio of the ammonia hydrogen peroxide solution mixture, the hydrogen peroxide solution flow rate changing step A3 is performed alone, the ammonia solution flow rate changing step A4 is performed alone, or the hydrogen peroxide solution flow rate is changed. This can be achieved by performing the step A3 and the ammonia water flow rate changing step A4 in parallel. When the hydrogen peroxide solution flow rate changing step A3 and the ammonia water flow rate changing step A4 are performed in parallel, the flow rate adjusting valves 101 and 103 are set so that the change in the hydrogen peroxide solution flow rate and the change in the ammonia water flow rate become asynchronous. Is preferably controlled. For example, if the ammonia water flow rate is decreased when the hydrogen peroxide water flow rate is increased, and the ammonia water flow rate is increased when the hydrogen peroxide water flow rate is decreased, the composition of the ammonia hydrogen peroxide water mixture can be reduced. A remarkable fluctuation can be given.

  In order to give fluctuation to the supply flow rate of the ammonia hydrogen peroxide solution mixture, for example, the hydrogen peroxide solution flow rate changing step A3, the ammonia water flow rate changing step A4, and the pure water flow rate changing step A7 may be performed in parallel. More specifically, the hydrogen peroxide water flow rate, the ammonia water flow rate, and the pure water flow rate are changed in synchronization. That is, the hydrogen peroxide water flow rate, the ammonia water flow rate, and the pure water flow rate are simultaneously decreased or increased. Thereby, fluctuations can be imparted to the flow rate of the ammonia hydrogen peroxide solution mixture supplied from the treatment liquid nozzle 2 to the surface of the substrate W.

In addition, by performing the hydrogen peroxide solution on / off step A1, the ammonia water on / off step A2 and the pure water on / off step in parallel, the ammonia hydrogen peroxide solution mixture is supplied intermittently. Thus, fluctuations can be imparted to the surface state of the substrate W.
If the pure water temperature switching step A6 is further combined, a remarkable fluctuation (fluctuation) can be caused by the state of the substrate W surface.

  Thus, the large fluctuation in the state of the surface of the substrate W causes fluctuation in the zeta potential of the substrate W and the particles on the surface thereof, and as a result, the particle removal effect by the ammonia hydrogen peroxide solution mixture can be enhanced. it can. Further, by performing the pure water temperature switching step A6, the substrate W expands and contracts, and as a result, the particle removal effect on the surface of the substrate W can be further enhanced.

Next, the HPM fluctuation applying step (step S7) will be described.
The HPM fluctuation imparting step includes at least one of the following steps B1 to B7. Of course, the HPM fluctuation imparting step may be performed by combining two or more of these steps and performing them sequentially or simultaneously.
B1: Hydrogen peroxide water on / off process B2: Hydrochloric acid on / off process B3: Hydrogen peroxide water flow rate changing process B4: Hydrochloric acid water flow rate changing process B5: Pure water on / off process B6: Pure water temperature switching process B7: Pure water flow rate changing step The hydrogen peroxide solution on / off step B1 can be performed in the same manner as the hydrogen peroxide solution on / off step A1 in the APM fluctuation applying step.

  The hydrochloric acid on / off step B2 is a step of switching between a state in which hydrochloric acid is supplied to the mixing unit 40 of the mixing valve 4 and a state in which the hydrochloric acid is not supplied by controlling opening and closing of the hydrochloric acid chemical introduction valve 42. For example, the opening / closing cycle of the chemical solution introduction valve 42 may be about 4 seconds (for example, it is opened for 2 seconds and then closed for 2 seconds). By this hydrochloric acid on / off process B2, hydrochloric acid is intermittently supplied to the mixing unit 40, and therefore, the supply of hydrochloric acid to the surface of the substrate W is also intermittent. As a result, the state of the surface of the substrate W changes in a short cycle, so that a remarkable change (fluctuation) can be given to the state of the surface of the substrate W.

The hydrogen peroxide solution flow rate changing step B3 can be performed in the same manner as the hydrogen peroxide solution flow rate changing step A3 in the APM fluctuation applying step.
The hydrochloric acid flow rate changing step B4 is a step of increasing or decreasing the flow rate of hydrochloric acid introduced into the mixing unit 40 of the mixing valve 4 by increasing or decreasing the opening degree of the hydrochloric acid flow rate adjusting valve 102. For example, the opening degree of the flow rate adjustment valve 102 may be increased or decreased with a period of about 5 seconds. The opening degree of the flow rate adjusting valve 102 may be increased or decreased continuously or may be increased or decreased stepwise. By this hydrochloric acid flow rate changing step B4, the supply flow rate of hydrochloric acid to the surface of the substrate W changes in a short cycle. Thereby, a remarkable change (fluctuation) can be given to the state of the substrate W surface. That is, the concentration of hydrochloric acid in the processing liquid supplied to the surface of the substrate W (in other words, the composition of the processing liquid) can be increased or decreased in a short cycle.

The pure water on / off process B5 can be performed in the same manner as the pure water on / off process A5 in the APM fluctuation applying process. The pure water temperature switching step B6 can be performed in the same manner as the pure water temperature switching step A6 in the APM fluctuation applying step. Furthermore, the pure water flow rate changing step B7 can be performed in the same manner as the pure water flow rate changing step A7 in the APM fluctuation applying step.
For example, in order to give fluctuation to the concentration of the hydrochloric acid / hydrogen peroxide solution mixture, the hydrogen peroxide solution flow rate changing step B3 and the hydrochloric acid flow rate changing step B4 may be performed in parallel. In this case, the hydrogen peroxide water flow rate and the hydrochloric acid flow rate are increased or decreased in synchronization. That is, the hydrochloric acid flow rate is increased when the hydrogen peroxide solution flow rate is increased, and the hydrochloric acid flow rate is also decreased when the hydrogen peroxide solution flow rate is decreased. Thereby, the density | concentration of hydrochloric acid hydrogen peroxide water liquid mixture can be increased / decreased. The concentration change need not be performed within a certain amplitude range. For example, the concentration of the hydrochloric acid / hydrogen peroxide solution mixed solution is gradually shifted to the high concentration side or the low concentration side while increasing / decreasing the concentration. The concentration can also be changed.

As described above, the fluctuation can be imparted to the concentration of the hydrochloric acid / hydrogen peroxide mixture by the pure water flow rate changing step B7.
In order to give fluctuation to the composition ratio of the hydrochloric acid / hydrogen peroxide solution mixture, the hydrogen peroxide solution flow rate changing step B3 is carried out alone, the hydrochloric acid flow rate changing step B4 is carried out alone, or the hydrogen peroxide solution flow rate changing step. B3 and the hydrochloric acid flow rate changing step B4 may be performed in parallel. When the hydrogen peroxide solution flow rate changing step B3 and the hydrochloric acid flow rate changing step B4 are performed in parallel, the flow rate adjustment valves 101 and 102 are controlled so that the change in the hydrogen peroxide solution flow rate and the change in the hydrochloric acid flow rate become asynchronous. It is preferable to do. For example, if the hydrochloric acid flow rate is decreased when the hydrogen peroxide water flow rate is increased, and the hydrochloric acid flow rate is increased when the hydrogen peroxide water flow rate is decreased, the composition of the hydrochloric acid hydrogen peroxide water mixture is remarkable. Can give fluctuations.

  In order to give fluctuation to the supply flow rate of the hydrochloric acid / hydrogen peroxide solution mixture, for example, the hydrogen peroxide solution flow rate changing step B3, the hydrochloric acid flow rate changing step B4, and the pure water flow rate changing step B7 may be performed in parallel. More specifically, the hydrogen peroxide water flow rate, the hydrochloric acid flow rate, and the pure water flow rate are changed in synchronization. That is, the hydrogen peroxide flow rate, the hydrochloric acid flow rate, and the pure water flow rate are simultaneously decreased or increased. Thereby, fluctuations can be imparted to the flow rate of the hydrochloric acid / hydrogen peroxide solution mixture supplied from the treatment liquid nozzle 2 to the surface of the substrate W.

In addition, the hydrogen peroxide solution mixture is intermittently supplied by performing the hydrogen peroxide solution on / off step B1, the hydrochloric acid on / off step B2, and the pure water on / off step in parallel. Further, fluctuations can be imparted to the state of the surface of the substrate W.
If the pure water temperature switching step B6 is further combined, a remarkable fluctuation (fluctuation) can be caused in the state of the substrate W surface.

As described above, since the surface of the substrate W is greatly fluctuated, the metal contamination removal effect by the hydrochloric acid / hydrogen peroxide mixture can be enhanced. Further, by performing the pure water temperature switching step A6, the substrate W expands and contracts, and as a result, the metal contamination removal effect on the surface of the substrate W can be further enhanced.
The hydrofluoric acid fluctuation imparting step (step S10) includes at least one of the following steps C1 to C5. Of course, the hydrofluoric acid fluctuation imparting step may be performed by combining two or more of these steps and performing them sequentially or simultaneously.

C1: Hydrofluoric acid on / off process C2: Hydrofluoric acid flow rate changing process C3: Pure water on / off process C4: Pure water temperature switching process C5: Pure water flow rate changing process Hydrofluoric acid on / off process C1 is for hydrofluoric acid This is a step of switching between a state where hydrofluoric acid is supplied to the mixing unit 40 of the mixing valve 4 and a state where it is not supplied by controlling the opening and closing of the chemical solution introduction valve 44. For example, the opening / closing cycle of the chemical solution introduction valve 42 may be about 5 seconds. By this hydrofluoric acid on / off step C1, hydrofluoric acid is intermittently supplied to the mixing unit 40, and therefore, the supply of hydrofluoric acid to the surface of the substrate W is also intermittent. As a result, the state of the surface of the substrate W changes in a short cycle, so that a remarkable change (fluctuation) can be given to the state of the surface of the substrate W.

  The hydrofluoric acid flow rate changing step C <b> 2 is a step of increasing or decreasing the flow rate of hydrofluoric acid introduced into the mixing unit 40 of the mixing valve 4 by increasing or decreasing the opening degree of the hydrofluoric acid flow rate adjusting valve 104. For example, the opening degree of the flow rate adjustment valve 104 may be increased or decreased with a period of about 10 seconds. The opening degree of the flow rate adjusting valve 104 may be increased or decreased continuously or in steps. By this hydrofluoric acid flow rate changing step C3, the supply flow rate of hydrofluoric acid to the surface of the substrate W changes in a short cycle. Thereby, a remarkable change (fluctuation) can be given to the state of the substrate W surface. That is, the concentration of hydrofluoric acid in the processing liquid supplied to the surface of the substrate W (in other words, the composition of the processing liquid) can be increased or decreased in a short cycle.

The pure water on / off process C3 can be performed in the same manner as the pure water on / off process A5 in the APM fluctuation applying process. The pure water temperature switching step C4 can be performed in the same manner as the pure water temperature switching step A6 in the APM fluctuation applying step. Furthermore, the pure water flow rate changing step C5 can be performed in the same manner as the pure water flow rate changing step A7 in the APM fluctuation applying step.
For example, in order to give fluctuation to the concentration of dilute hydrofluoric acid, the hydrofluoric acid flow rate changing step C2 may be performed. The concentration does not need to be changed within a certain amplitude range. For example, the concentration of dilute hydrofluoric acid is changed so as to gradually shift to a high concentration side or a low concentration side while increasing or decreasing the concentration. You can also. As described above, the application of fluctuation to the concentration of dilute hydrofluoric acid can also be performed by the pure water flow rate changing step C5. Since the composition of the dilute hydrofluoric acid varies depending on the concentration of hydrofluoric acid, the step of giving fluctuations to the concentration of dilute hydrofluoric acid is also the step of giving fluctuations to the composition of dilute hydrofluoric acid.

  In order to give fluctuation to the supply flow rate of dilute hydrofluoric acid, for example, the hydrofluoric acid flow rate changing step C2 and the pure water flow rate changing step C5 may be performed in parallel. More specifically, the hydrofluoric acid flow rate and the pure water flow rate are changed synchronously. That is, the hydrofluoric acid flow rate and the pure water flow rate are simultaneously decreased or increased. Thereby, fluctuations can be imparted to the flow rate of dilute hydrofluoric acid supplied from the processing liquid nozzle 2 to the surface of the substrate W.

In addition, by performing the hydrofluoric acid on / off step C1 and the pure water on / off step in parallel, the dilute hydrofluoric acid is supplied intermittently, and the state of the surface of the substrate W can be given fluctuation. it can.
If the pure water temperature switching step C4 is further combined, a remarkable fluctuation (fluctuation) can be caused in the state of the substrate W surface.

  In this way, the large fluctuation in the surface state of the substrate W can enhance the natural oxide film removal effect by dilute hydrofluoric acid. Since dilute hydrofluoric acid also has a metal decontamination effect, this metal decontamination effect is also enhanced. Further, by performing the pure water temperature switching step C4, the substrate W is expanded and contracted. As a result, the natural oxide film removing effect and the metal contamination removing effect on the surface of the substrate W can be further enhanced.

The rinse fluctuation imparting step (step S12) includes at least one of the following steps D1 to D3. Of course, the rinse fluctuation applying step may be performed by combining two or more of these steps and performing them sequentially or simultaneously.
D1: Pure water on / off process D2: Pure water temperature switching process D3: Pure water flow rate changing process The pure water on / off process D1 can be performed in the same manner as the pure water on / off process A5 in the APM fluctuation application process. The pure water temperature switching step D2 can be performed in the same manner as the pure water temperature switching step A6 in the APM fluctuation applying step. Furthermore, the pure water flow rate changing step D3 can be performed in the same manner as the pure water flow rate changing step A7 in the APM fluctuation applying step.

By performing these steps D1 to D3 alone or in combination of two or more, a large fluctuation occurs in the state of the surface of the substrate W during the rinsing step. Thereby, the chemical solution on the substrate W can be efficiently washed away and removed out of the substrate W.
As described above, in this embodiment, in the treatment process using the ammonia hydrogen peroxide solution, the treatment process using the hydrochloric acid hydrogen peroxide solution, and the final rinsing process, processing such as fluctuation in the supply flow rate of the treatment liquid and on / off of the treatment liquid supply Fluctuations are given to process parameters related to the physical force of the liquid, and fluctuations are given to process parameters related to the activity of the processing liquid such as the concentration and temperature of the processing liquid. As a result, the efficiency of the chemical treatment and the rinsing treatment can be increased, and high-quality substrate processing becomes possible.

In addition, as a process parameter regarding the physical force of the processing liquid, the pressure of the processing liquid can be cited. In order to vary the impact force when the processing liquid hits the substrate W by applying fluctuations to the pressure of the processing liquid, fluctuations are applied to the adjustment pressures of the regulators 53 and 78, or fluctuations are applied to the processing liquid flow rate. do it.
FIG. 4 is an illustrative view for explaining the configuration of a substrate processing apparatus according to another embodiment of the present invention. In FIG. 4, portions corresponding to the respective portions shown in FIG. 1 described above are denoted by the same reference numerals, and description thereof is omitted. Reference is also made to FIG.

The substrate processing apparatus of this embodiment is for performing a resist stripping process for stripping a used resist used as a mask for dry etching or ion implantation from the surface of a substrate W.
In this embodiment, the mixing valve 4 includes a mixing unit 40 having two introduction ports (inlets) and two chemical solution introduction valves 41 and 42 connected to the two introduction ports. A chemical solution supply source 71 for supplying hydrogen peroxide solution is connected to the chemical solution introduction path 61 connected to the chemical solution introduction valve 41. A chemical solution supply source 72 for supplying sulfuric acid (for example, concentrated sulfuric acid heated to 80 ° C.) is connected to the chemical solution introduction path 62 connected to the chemical solution introduction valve 42. With this configuration, the mixing valve 4 mixes hydrogen peroxide water and sulfuric acid to generate a sulfuric acid / hydrogen peroxide mixture (SPM), which is led to the treatment liquid supply path 3. be able to.

The processing liquid supply path 3 is branched into two branch pipes 31 and 32 by a three-way valve 30 controlled by the control device 7, and these are joined before the processing liquid nozzle 2. A flow pipe 33 with a stirring fin is interposed in one branch pipe 31, and a flow pipe 33 with a stirring fin is not interposed in the other branch pipe 32.
The stirring fin-equipped flow pipe 33 includes a plurality of stirring fins each formed of a rectangular plate-like body added with a twist of about 180 degrees around the liquid flow direction in the pipe member, around the central axis of the pipe along the liquid flow direction. The rotation angle is changed by 90 degrees alternately and arranged along the tube axis direction. For example, the product name “MX Series: Inline Mixer” manufactured by Noritake Company Limited Advance Electric Industries, Ltd. Can be used.

When the chemical solution introduction valves 41 and 42 are opened, sulfuric acid and hydrogen peroxide solution are combined and mixed in the mixing valve 4, and a chemical reaction between sulfuric acid and hydrogen peroxide solution (H ₂ SO ₄ + H ₂ O ₂ → H ₂ SO). ₅ + H ₂ O) is generated, and a resist stripping solution (SPM: sulfuric acid / hydrogen peroxide solution mixed solution) containing caloic acid (H ₂ SO ₅ ) having strong oxidizing power is generated. Of course, the higher the degree of mixing, the more caloic acid is produced and the oxidizing power increases. In addition, the higher the degree of mixing, the more heat generated by the chemical reaction (reaction heat) occurs, and due to this heat generation, the temperature of the resist stripping solution is high enough to remove the resist from the substrate W (for example, 80 ° C). It rises reliably to -150 degreeC.

  If the sulfuric acid and the hydrogen peroxide solution are simply joined by the mixing valve 4, the sulfuric acid and the hydrogen peroxide solution are not sufficiently mixed. Therefore, by passing the sulfuric acid and hydrogen peroxide solution merged at the mixing valve 4 through the flow pipe 33 with stirring fins, the mixing of sulfuric acid and hydrogen peroxide solution is promoted, and the mixed solution is sufficiently uniformly stirred. be able to.

  By switching the three-way valve 30, the treatment liquid nozzle 2 passes through the branch pipe 32 and the resist stripping liquid having a relatively high activity sufficiently stirred by the flow pipe 33 with the stirring fin interposed in the branch pipe 31. Thus, it is possible to select and supply a resist stripping solution having a relatively low activity that bypasses the flow pipe 33 with stirring fins. Therefore, fluctuations can be imparted to the activity of the resist stripping solution supplied to the surface of the substrate W by periodically switching the three-way valve 30 by the control device 7 (see FIG. 2).

  On the other hand, in this embodiment, a rinse liquid nozzle 9 is provided separately from the processing liquid nozzle 2. A pure water introduction path 5 is connected to the rinsing liquid nozzle 9. As a result, a rinsing process can be performed by supplying pure water onto the substrate W in a separate system from the resist stripping solution. The rinse liquid nozzle 9 may be a scan nozzle that moves horizontally along the surface of the substrate W, or may be a fixed nozzle that discharges the rinse liquid from the fixed position toward the vicinity of the rotation center of the substrate W.

  FIG. 5 is a flowchart for explaining an example of processing for one substrate W. When the substrate W to be processed is loaded into the spin chuck 1 (step S21), the control device 7 drives the rotation drive mechanism 14 to rotate the substrate W at a predetermined liquid processing speed (step S22). At this time, the chemical solution introduction valves 41 and 42, the pure water supply source valve 51, the warm pure water supply source valve 52, and the pure water valve 55 are all controlled to be closed.

  When the rotation speed of the substrate W reaches the liquid processing speed, the control device 7 controls the chemical liquid introduction valve 41 for hydrogen peroxide solution and the chemical liquid introduction valve 42 for sulfuric acid, so that the substrate W is removed from the processing liquid nozzle 2. A sulfuric acid / hydrogen peroxide mixture (SPM) as a resist stripping solution is discharged onto the surface of the substrate (step S23). More specifically, the mixing ratio corresponding to the ratio (flow rate ratio) of the hydrogen peroxide solution flow rate through the chemical solution introduction channel 61 and the sulfuric acid flow rate through the chemical solution introduction channel 62 by opening the chemical solution introduction valves 41 and 42. In (composition ratio), a hydrogen peroxide solution and sulfuric acid are mixed to prepare a resist stripping solution comprising a sulfuric acid hydrogen peroxide solution mixture. The prepared resist stripping solution is sent to the processing solution nozzle 2 through the processing solution supply path 3 and is discharged toward the surface of the rotating substrate W. In this way, the resist stripping liquid is discharged onto the surface of the substrate W, whereby the resist on the surface of the substrate W is stripped.

During the period in which the resist stripping solution is supplied to the substrate W, a resist stripping fluctuation applying step for applying fluctuation to the processing conditions by the resist stripping solution is performed (step S24). Details of this resist peeling fluctuation applying step will be described later.
After the processing with the resist stripping solution is performed for a predetermined time, the control device 7 closes the chemical solution introduction valves 41 and 42. Thereby, the discharge of the resist stripping liquid from the processing liquid nozzle 2 is stopped (step S25).

  Next, the control device 7 opens the pure water supply source valve 51 or the warm pure water supply source valve 52 and further opens the pure water valve 55. Thereby, pure water (room temperature or a temperature higher than room temperature) is supplied from the pure water introduction path 5 to the rinsing liquid nozzle 9, and the pure water is discharged toward the surface of the substrate W rotated by the spin chuck 1. Is done. Thus, a rinsing process for washing away the resist stripping solution on the substrate W and removing it from the substrate W is performed (step S26).

During the period of the rinsing process, a rinse fluctuation imparting process for imparting fluctuations to the rinsing process conditions is performed (step S27). This rinse fluctuation application process may be a process similar to the rinse fluctuation application process (step S12 in FIG. 3) in the first embodiment described above, for example.
When the rinsing process while applying fluctuation is performed over a predetermined period, the control device 7 closes the pure water valve 55 and stops the discharge of the pure water from the rinsing liquid nozzle 9. Further, the control device 7 controls the rotation drive mechanism 14 to accelerate the rotation speed of the substrate W by the spin chuck 1 to a predetermined drying speed (for example, 3000 rpm). As a result, a drying process is performed in which the pure water adhering to the surface of the substrate W after cleaning is spun off by centrifugal force and dried (step S28).

When this drying process is completed, the rotation of the substrate W by the spin chuck 1 is stopped, and the processed substrate W is unloaded from the spin chuck 1 by a transfer robot (not shown) (step S29).
The resist peeling fluctuation applying step includes at least one of the following steps E1 to E5. Of course, the resist peeling fluctuation applying step may be performed by combining two or more of these steps and performing them sequentially or simultaneously.

E1: Hydrogen peroxide water on / off process E2: Sulfuric acid on / off process E3: Hydrogen peroxide water flow rate changing process E4: Sulfuric acid flow rate changing process E5: Mixing degree changing process Hydrogen peroxide water on / off process E1 This is a step of switching between the state in which the hydrogen peroxide solution is supplied to the mixing unit 40 of the mixing valve 4 and the state in which the hydrogen peroxide solution is not supplied by controlling the opening and closing of the hydrogen oxide water chemical solution introduction valve 41. For example, the opening / closing cycle of the chemical solution introduction valve 41 may be about 4 seconds (for example, it is opened for 2 seconds and then closed for 2 seconds). By the hydrogen peroxide solution on / off process E1, the hydrogen peroxide solution is intermittently supplied to the mixing unit 40, and therefore, the supply of the hydrogen peroxide solution to the surface of the substrate W is also intermittent. As a result, the state of the surface of the substrate W changes in a short cycle, so that a significant change (fluctuation) can be given to the state of the surface of the substrate W.

  The sulfuric acid on / off process E2 is a process of switching between a state in which sulfuric acid is supplied to the mixing unit 40 of the mixing valve 4 and a state in which the sulfuric acid is not supplied by controlling the opening and closing of the chemical liquid introduction valve 42 for sulfuric acid. For example, the opening / closing cycle of the chemical solution introduction valve 42 may be about 4 seconds (for example, it is opened for 2 seconds and then closed for 2 seconds). By this sulfuric acid on / off process E2, sulfuric acid is intermittently supplied to the mixing unit 40, and therefore, the supply of sulfuric acid to the surface of the substrate W is also intermittent. As a result, the state of the surface of the substrate W changes in a short cycle, so that a remarkable change (fluctuation) can be given to the state of the surface of the substrate W.

  The hydrogen peroxide flow rate changing step E3 is a step of increasing or decreasing the flow rate of the hydrogen peroxide solution introduced into the mixing unit 40 of the mixing valve 4 by increasing or decreasing the opening degree of the hydrogen peroxide flow rate adjusting valve 101. is there. For example, the opening degree of the flow rate adjustment valve 101 may be increased or decreased with a period of about 5 seconds. The opening degree of the flow rate adjusting valve 101 may be increased or decreased continuously or may be increased or decreased stepwise. By the hydrogen peroxide solution flow rate changing step E3, the supply flow rate of the hydrogen peroxide solution to the surface of the substrate W is changed in a short cycle. Thereby, a remarkable change (fluctuation) can be given to the state of the substrate W surface. That is, the concentration of the hydrogen peroxide solution in the resist stripping solution supplied to the surface of the substrate W (in other words, the composition of the processing solution) can be increased or decreased in a short cycle.

  The sulfuric acid flow rate changing step E4 is a step of increasing or decreasing the flow rate of sulfuric acid introduced into the mixing unit 40 of the mixing valve 4 by increasing or decreasing the opening degree of the sulfuric acid flow rate adjusting valve 102. For example, the opening degree of the flow rate adjustment valve 102 may be increased or decreased with a period of about 5 seconds. The opening degree of the flow rate adjusting valve 102 may be increased or decreased continuously or may be increased or decreased stepwise. By this sulfuric acid flow rate changing step E4, the supply flow rate of sulfuric acid to the surface of the substrate W is changed in a short cycle. Thereby, a remarkable change (fluctuation) can be given to the state of the substrate W surface. That is, the sulfuric acid concentration (in other words, the composition of the processing liquid) in the resist stripping solution supplied to the surface of the substrate W can be increased or decreased in a short cycle.

  In the mixing degree changing step E5, the control device 7 controls the three-way valve 30 and switches the flow path of the resist stripping solution between the branch pipe 31 side and the branch pipe 32 side. This is a step of switching between a state in which the resist stripping solution is supplied to the substrate W without stirring and a state in which the resist stripping solution is supplied to the substrate W without stirring. The switching cycle of the three-way valve 30 is preferably about 4 seconds (for example, it opens on the branch pipe 32 side for 2 seconds and then opens on the branch pipe 32 side for 2 seconds). Thereby, since the mixing degree (stirring degree) of the resist stripping solution supplied to the surface of the substrate W changes with time in a short cycle, the activity of the resist stripping solution on the surface of the substrate W can be fluctuated. In addition, since the reaction heat generated fluctuates as a result of the difference in the degree of mixing of the resist stripping solution, thermal expansion and thermal contraction of the substrate W occur accordingly. In this way, fluctuations can be imparted to the state of the substrate W surface.

  For example, in order to give fluctuation to the composition ratio of the resist stripping solution, the hydrogen peroxide solution flow rate changing step E3 is performed alone, the sulfuric acid flow rate changing step E4 is performed alone, the hydrogen peroxide solution flow rate changing step E3 and The sulfuric acid flow rate changing step E4 may be performed in parallel. When the hydrogen peroxide solution flow rate changing step E3 and the sulfuric acid flow rate changing step E4 are performed in parallel, the flow rate adjusting valves 101 and 102 are controlled so that the change in the hydrogen peroxide solution flow rate and the change in the sulfuric acid flow rate become asynchronous. It is preferable to do. For example, if the sulfuric acid flow rate is decreased when the hydrogen peroxide water flow rate is increased, and the sulfuric acid flow rate is increased when the hydrogen peroxide water flow rate is decreased, the composition of the sulfuric acid hydrogen peroxide water mixture is remarkable. Can give fluctuations.

  In order to give fluctuation to the supply flow rate of the sulfuric acid hydrogen peroxide solution mixture, for example, the hydrogen peroxide solution flow rate changing step E3 and the sulfuric acid flow rate changing step E4 may be performed in parallel. More specifically, the hydrogen peroxide water flow rate and the sulfuric acid flow rate are changed in synchronization. That is, the hydrogen peroxide solution flow rate and the sulfuric acid flow rate are simultaneously decreased or increased. As a result, fluctuations can be imparted to the flow rate of the sulfuric acid / hydrogen peroxide mixture supplied from the treatment liquid nozzle 2 to the surface of the substrate W.

In addition, the hydrogen peroxide solution ON / OFF step E1 and the sulfuric acid ON / OFF step E2 are performed in parallel, so that the mixed solution of sulfuric acid and hydrogen peroxide solution is intermittently supplied to bring the surface of the substrate W into a state. Fluctuation can also be added.
If the degree-of-mixing change step E5 is further combined, a remarkable fluctuation (fluctuation) can be caused in the state of the substrate W surface.

As a result of such large fluctuations in the state of the substrate W surface, fluctuations occur in the state of the substrate W and the resist film on the surface thereof. As a result, the resist stripping process can be performed efficiently.
As mentioned above, although two embodiment of this invention was described, this invention can also be implemented with another form. For example, in the first embodiment described above, fluctuations may be imparted to the state of pure water as the rinsing liquid also in the first and / or second intermediate rinsing steps (steps S5 and S8 in FIG. 3). Good.

  Moreover, although the above-mentioned embodiment demonstrated the example which changes the temperature of a pure water, it is good also as a structure which gives fluctuation to the temperature of a chemical | medical solution stock solution. For example, a plurality of the same type of chemical solution stocks having different temperatures can be introduced into the mixing valve 4 via the chemical solution introduction valve, and the chemical solution stock solution at any temperature is selected and introduced into the mixing unit 40 of the mixing valve 4. You just have to do it.

In addition, when changing the concentration of the chemical solution, the same type of chemical solution stock solution having different concentrations can be selectively introduced to the mixing valve 4 via the chemical solution introduction valve, and the chemical solution stock solution of any concentration is selected. Then, it may be introduced into the mixing section 40 of the mixing valve 4 .

  The present invention can also be applied to substrate processing using a two-fluid nozzle that generates a droplet jet by mixing gas and liquid. In this case, for example, fluctuations may be imparted to the flow rate of the gas and / or liquid supplied to the two-fluid nozzle. Further, fluctuations may be imparted to the temperature of the gas and / or liquid supplied to the two-fluid nozzle. Further, fluctuation may be imparted to the concentration of the liquid supplied to the two-fluid nozzle. Furthermore, the gas and / or liquid supplied to the two-fluid nozzle may be controlled on / off. Specifically, only the gas may be on / off controlled to alternately switch between a state where the droplet jet is supplied to the substrate and a state where the liquid flows out from the nozzle and reaches the substrate surface. Alternatively, the gas and liquid may be simultaneously turned on / off to switch between a state where the droplet jet is supplied and a state where the droplet jet is not supplied.

  In addition, various design changes can be made within the scope of matters described in the claims.

It is a figure which simplifies and shows the structure of the substrate processing apparatus which concerns on one Embodiment of this invention. It is a block diagram which shows the electric constitution of the said substrate processing apparatus. It is a flowchart for demonstrating an example of the process process with respect to a board | substrate. It is an illustration figure for demonstrating the structure of the substrate processing apparatus which concerns on other embodiment of this invention. 6 is a flowchart for explaining an example of processing by the apparatus of FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Spin chuck 2 Process liquid nozzle 3 Process liquid supply path 4 Mixing valve 5 Pure water introduction path 7 Control apparatus 9 Rinse liquid nozzle 11 Spin axis 12 Spin base 13 Holding member 14 Rotation drive mechanism 30 Three-way valve 31 Branch pipe 32 Branch pipe 33 Flow pipe with stirring fin 40 Mixing section 41 to 44 Chemical solution introduction valve 51 Pure water supply source valve 52 Warm pure water supply source valve 53 Regulator 54 Flow meter 55 Pure water valve 56 Pressure gauge 61 to 64 Chemical solution introduction path 71 to 74 Chemical solution supply source 75 Chemical solution stock 76 Chemical solution tank 77 Nitrogen gas supply path 78 Regulator 79 Nitrogen gas valve 81-84 Filter 86-89 Pressure gauge 91-94 Flow meter 101-104 Flow control valve W Substrate

Claims (10)

A processing liquid supplying step of the processing solution to perform processing to supply paper to the substrate relative to the substrate,
During the processing liquid supply process, a fluctuation that can cause a change in the state of the substrate surface without impairing the target substrate processing is given to the process parameter related to the processing liquid supplied to the substrate. A substrate processing method including a fluctuation imparting step. The substrate processing method according to claim 1, wherein the process parameter includes a parameter related to an activity of the processing liquid . The substrate processing method according to claim 2, wherein the parameter relating to the activity includes at least one of a temperature and a concentration of a processing solution . The treatment liquid is a mixed liquid prepared by mixing a plurality of types of liquids ,
The substrate processing method according to claim 2, wherein the parameter relating to the activity includes a mixing degree of the mixed solution . The substrate processing method according to claim 1, wherein the process parameter includes a parameter related to a physical force of a processing liquid . The substrate processing method according to claim 5, wherein the parameter relating to the physical force includes at least one of a temperature, a flow rate, and a pressure of a processing liquid . The treatment liquid is a mixed liquid prepared by mixing a plurality of types of liquids ,
The substrate processing method according to claim 1, wherein the process parameter includes a composition ratio of the mixed solution .   The substrate processing method according to claim 1, wherein the fluctuation applying step includes a step of repeatedly increasing and decreasing a process parameter.   The substrate processing method according to claim 1, wherein the fluctuation applying step includes a step of periodically increasing and decreasing process parameters. A treatment liquid supply means for supply supplying the substrate treatment liquid for performing the process on the substrate,
To the process parameters related to the processing solution supply means for supplying processing liquid, does not inhibit the substrate processing of interest, and the fluctuation imparting means for imparting fluctuation that can produce a change in the state of the substrate surface Including a substrate processing apparatus.

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