JP2014130872A - Substrate processing apparatus, and substrate processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent damages of a substrate due to movement of electric charges during processing by a process liquid.SOLUTION: In a substrate processing apparatus 10, a temperature of an electricity removal liquid in which its specific resistance gradually decreases with an increase in the liquid temperature, is controlled by a temperature control part 61, and the specific resistance of the electricity removal liquid becomes larger than that of a processing liquid (SPM liquid) used for the processing in a sheet processing apparatus 1. The electricity removal liquid is reserved in an electricity removal liquid reservoir part 71. Then a plurality of substrates 9 held by a cartridge 73, are immersed in the electricity removal liquid inside the electricity removal liquid reservoir part 71, and main surfaces on both sides of the substrates 9 are brought into contact with the electricity removal liquid over the entire surfaces. Thus, electricity is removed relatively gently from the substrates 9. Then, after the end of electricity removal processing and the drying processing by a substrate drying part 75, in the sheet processing apparatus 1, the SPM liquid is supplied onto an upper surface 91 of the substrate 9, and SPM processing is performed. Thus, during the SPM processing, a large amount of electric charges are prevented from rapidly moving from the substrate 9 to the SPM liquid, and damages of the substrate 9 are prevented.

Description

  The present invention relates to a technique for processing a substrate.

  Conventionally, in a manufacturing process of a semiconductor substrate (hereinafter simply referred to as “substrate”), various processes are performed on a substrate having an insulating film such as an oxide film using a substrate processing apparatus. For example, by supplying a chemical solution to a substrate having a resist pattern formed on the surface, a process such as etching is performed on the surface of the substrate. Further, after the etching or the like is completed, a process for removing the resist on the substrate is also performed.

  In the substrate processing apparatus of Patent Document 1, before processing with a chemical solution such as an SPM (sulfuric acid / hydrogen peroxide mixture) solution, a liquid having a lower electrical conductivity than the chemical solution is supplied to the processing region on the substrate, and the liquid Is present on the processing region, and the chemical solution is discharged to the processing region. As a result, local damage to the substrate caused by contact between the substrate and the chemical solution can be prevented. The local damage of the substrate is the local destruction of the field oxide film and the gate oxide film in the processing region, and the destruction is caused by the fact that the chemical solution is charged by the frictional charging phenomenon between the chemical solution and the chemical solution nozzle. It occurs by contacting the processing area of the substrate.

In Patent Document 2, before supplying a chemical solution such as concentrated sulfuric acid to the processing region on the wafer, a liquid such as CO ₂ water having a specific resistance lower than that of the chemical solution is supplied to the processing region. A technique is disclosed in which a chemical solution is ejected to a processing region in the existing state. As a result, it is possible to prevent charging due to an electrostatic friction phenomenon that occurs when the chemical solution comes into contact with the processing region.

  Patent Document 3 discloses a technique for discharging static electricity present on a surface of a substrate or a chemical nozzle by supplying ionized vapor to the surface of the substrate or a chemical nozzle in an electronic device cleaning apparatus. In the substrate liquid processing apparatus of Patent Document 4, a charge removal process step of discharging a charge removal treatment liquid toward the surface opposite to the circuit formation surface of the substrate is performed before the liquid treatment step with respect to the circuit formation surface of the substrate. .

  On the other hand, Patent Document 5 discloses a substrate processing apparatus that removes organic substances adhering to the surface of a substrate by supplying a removing liquid to the surface of the substrate. In the substrate processing apparatus, temperature adjusting means for adjusting the temperature of the substrate is provided so that the difference between the temperature of the substrate and the temperature of the removing liquid supplied onto the substrate is within a predetermined range. As an example of the temperature adjusting means, there is a fluid supply means for supplying a fluid whose temperature is adjusted to the back surface of the substrate held by the holding and rotating means.

JP 2009-200365 A JP 2007-134673 A JP 2007-214347 A JP 2011-103438 A JP 2004-158588 A

  By the way, the substrate processed by the substrate processing apparatus is subjected to a dry process such as dry etching or plasma CVD (Chemical Vapor Deposition) before being carried into the substrate processing apparatus. In such a dry process, since charges are generated in the device and charged, the substrate is carried into the substrate processing apparatus in a charged state (so-called carry-in charging). In the substrate processing apparatus, when a chemical solution having a small specific resistance such as an SPM solution is supplied onto the substrate, the electric charge in the device rapidly moves from the device to the chemical solution (that is, discharges into the chemical solution). ), The device may be damaged by the heat generated by the movement. In view of this, it is conceivable to neutralize the substrate with an ionizer before supplying the chemical solution to the substrate. However, it is difficult to efficiently eliminate the charge when the charge amount of the substrate is large.

  The present invention has been made in view of the above problems, and an object of the present invention is to prevent damage to a substrate due to movement of electric charges during processing with a processing liquid.

  The invention according to claim 1 is a substrate processing apparatus for processing a substrate, wherein the substrate holding unit that holds the substrate, and the process of supplying the processing liquid onto the first main surface that is one main surface of the substrate. A liquid-removing liquid-contacting section that brings the liquid supply section into contact with the liquid-removing liquid whose specific resistance gradually decreases as the liquid temperature rises, and the second main surface that is the first main surface and the other main surface of the substrate; By controlling the temperature adjusting unit that adjusts the temperature of the static elimination liquid, the treatment liquid supply unit, the static elimination liquid wetted part, and the temperature adjustment unit, the temperature of the static elimination liquid is determined by the specific resistance of the static elimination liquid. By maintaining the liquid contact state by bringing the first main surface and the second main surface of the substrate into contact with the charge-removing solution over the entire surface within a range larger than the specific resistance of the treatment liquid. After reducing the charge on the substrate, the treatment liquid is applied to the first main surface of the substrate. It is supplied to a control unit for performing predetermined processing.

  Invention of Claim 2 is a substrate processing apparatus of Claim 1, Comprising: The said static elimination liquid which contacts the said 1st main surface, and the said static elimination liquid which contacts the said 2nd main surface are on the said board | substrate. Is continuous.

  Invention of Claim 3 is a substrate processing apparatus of Claim 2, Comprising: The said static elimination liquid contact part is equipped with the static elimination liquid storage part which stores the said static elimination liquid, The said board | substrate is said static elimination liquid The first main surface and the second main surface are in contact with the charge removal liquid by being immersed in the charge removal liquid stored in the storage section.

  Invention of Claim 4 is a substrate processing apparatus of Claim 3, Comprising: The said normalization direction of each main surface is included in the said static elimination liquid stored in the said static elimination liquid storage part including the said board | substrate. A plurality of substrates arranged in the horizontal direction are immersed.

  Invention of Claim 5 is the substrate processing apparatus of Claim 1, Comprising: The said static elimination liquid contact part was hold | maintained at the said board | substrate holding part in the state which faced the said 1st main surface upwards A first discharge liquid contact portion that supplies the charge removal liquid onto the first main surface of the substrate and paddles the entire first main surface with the charge removal solution, and is opposed to the second main surface of the substrate. And a second discharging liquid contact portion that discharges the discharging liquid toward the second main surface and brings the entire second main surface into contact with the discharging solution.

  A sixth aspect of the present invention is the substrate processing apparatus according to any one of the first to fifth aspects, further comprising a static elimination liquid measuring unit that measures a temperature of the static elimination liquid, wherein the control unit includes the static elimination liquid. Based on the measurement result of the liquid measuring unit, the temperature adjusting unit is controlled so that the difference between the temperature of the static eliminating liquid and a predetermined target temperature is reduced.

  A seventh aspect of the present invention is the substrate processing apparatus according to the sixth aspect, wherein when the difference between the temperature of the static elimination liquid and the target temperature is equal to or less than a threshold temperature difference, the static elimination liquid by the temperature adjustment unit The temperature adjustment of is stopped.

  The invention according to claim 8 is the substrate processing apparatus according to claim 6 or 7, wherein a lower target temperature is set as a size of a device formed in advance on the substrate is smaller. .

  Invention of Claim 9 is a substrate processing apparatus in any one of Claim 1 thru | or 5, Comprising: The static elimination liquid measurement part which measures the specific resistance of the said static elimination liquid is further provided, The said control part is the said control part, Based on the measurement result of the neutralization liquid measurement unit, the temperature adjustment unit is controlled so that the difference between the specific resistance of the neutralization liquid and a predetermined target specific resistance becomes small.

  A tenth aspect of the present invention is the substrate processing apparatus according to the ninth aspect, wherein when the difference between the specific resistance of the static elimination liquid and the target specific resistance is equal to or less than a threshold specific resistance difference, the temperature adjusting unit The temperature adjustment of the neutralizing liquid is stopped.

  The invention according to claim 11 is the substrate processing apparatus according to claim 9 or 10, wherein the smaller the size of a device formed in advance on the substrate, the higher the target specific resistance is set. Is done.

  A twelfth aspect of the present invention is the substrate processing apparatus according to any one of the first to eleventh aspects, further comprising a liquid removing unit that removes the liquid on the first main surface of the substrate, and the control. When the unit controls the liquid removing unit, the neutralizing liquid is removed from the first main surface between the contact of the substrate with the neutralizing liquid and the predetermined treatment with the processing liquid. .

  A thirteenth aspect of the present invention is the substrate processing apparatus according to any one of the first to twelfth aspects, wherein the charge removal liquid is pure water.

  The invention according to claim 14 is the substrate processing apparatus according to any one of claims 1 to 13, wherein the processing solution contains sulfuric acid.

  The invention according to claim 15 is a substrate processing method for processing a substrate, wherein: a) the temperature of the static elimination liquid gradually decreasing as the liquid temperature rises, and the specific resistance of the static elimination liquid is equal to that of the processing liquid. A step in which the specific resistance is larger than the specific resistance; and b) after the step a), the main surfaces on both sides of the substrate are brought into contact with the charge removal solution over the entire surface to maintain the liquid contact state. A step of reducing the charge on the substrate, and c) a step of supplying the treatment liquid onto one main surface of the substrate and performing a predetermined treatment after the step b).

  A sixteenth aspect of the present invention is the substrate processing method according to the fifteenth aspect, wherein the neutralizing liquid that contacts the one main surface of the substrate and the neutralizing liquid that contacts the other main surface of the substrate. Are continuous on the substrate.

  Invention of Claim 17 is the substrate processing method of Claim 16, Comprising: In said b) process, the said board | substrate is immersed in the said static elimination liquid stored in the static elimination liquid storage part, The one main surface and the other main surface are in contact with the static elimination liquid.

  The invention according to claim 18 is the substrate processing method according to claim 17, wherein, in the step b), the charge removal liquid stored in the charge removal liquid storage section includes the substrate and each of the main processes. A plurality of substrates arranged so that the normal direction of the surface faces the horizontal direction is immersed.

  The invention according to claim 19 is the substrate processing method according to claim 15, wherein the step b) includes the step of b1) holding the one main surface upward. Supplying the neutralizing liquid onto the main surface of the substrate and paddle the entire one main surface with the neutralizing liquid; b2) discharging the neutralizing liquid toward the other main surface of the substrate and And a step of bringing the entire main surface of the liquid crystal into contact with the static elimination liquid.

  The invention described in claim 20 is the substrate processing method according to any one of claims 15 to 19, wherein the step a) includes a1) a step of measuring the temperature of the charge removal solution, and a2) the a1. ) A step of adjusting the temperature of the static elimination liquid so that a difference between the temperature of the static elimination liquid and a predetermined target temperature is reduced based on the measurement result in the step; a3) the a1) step and the a2) step; The process of repeating.

  A twenty-first aspect of the present invention is the substrate processing method according to any one of the fifteenth to nineteenth aspects, wherein the step a) includes a1) a step of measuring the temperature of the charge removal solution, and a2) the a1. ) Based on the measurement result in the step, if the difference between the temperature of the static elimination liquid and a predetermined target temperature is equal to or less than the threshold temperature difference, the temperature of the static elimination liquid is not adjusted and the temperature of the static elimination liquid and the target temperature are not adjusted. A step of adjusting the temperature of the static elimination liquid so that the difference between the temperature of the static elimination liquid and the target temperature is small when the difference is larger than the threshold temperature difference.

  The invention according to claim 22 is the substrate processing method according to claim 20 or 21, wherein a lower target temperature is set as the size of a device formed in advance on the substrate is smaller. .

  The invention described in claim 23 is the substrate processing method according to any one of claims 20 to 22, wherein d1) a step of obtaining a specific resistance of the processing solution before the step a), d2 ) Based on the relationship obtained in the step d3) d2), the specific resistance of the static elimination liquid is equal to the specific resistance of the treatment liquid. A step of acquiring the temperature of the static elimination liquid, d4) a step of setting a temporary target temperature lower than the temperature acquired in the step of d3), and d5) a step of preparing a static elimination liquid at the temporary target temperature; D6) reducing the charge on the test substrate by bringing the main surfaces on both sides of the test substrate into contact with the static elimination liquid at the temporary target temperature over the entire surface to maintain the liquid contact state; d7 ) Supply the treatment liquid onto one main surface of the test substrate. A step of performing the predetermined processing; d8) a step of evaluating the state of the one main surface of the test substrate after completion of the step d7); and d9) a state of the one main surface being good. For example, the temporary target temperature is set as the target temperature, and if the state of the one main surface is not good, the temporary target temperature is lowered until the state of the one main surface becomes good, and the d5) And the step d8) are repeated to further determine the temporary target temperature when the state becomes good as the target temperature.

  A twenty-fourth aspect of the present invention is the substrate processing method according to any one of the twenty-second to twenty-second aspects, wherein d1) a step of obtaining a specific resistance of the processing solution before the step a), d2 ) Obtained by the step of setting a temporary target specific resistance higher than the specific resistance of the treatment liquid, d3) the step of obtaining the relationship between the temperature of the static elimination liquid and the specific resistance, and d4) the step of d3). A step of obtaining, as a temporary target temperature, a temperature of the static elimination liquid at which the specific resistance of the static elimination liquid becomes equal to the temporary target specific resistance set in the step d2) based on the relationship; d5) the temporary target A step of preparing a temperature neutralizing solution; and d6) on the test substrate by maintaining the liquid contact state by bringing the principal surfaces on both sides of the test substrate into contact with the neutralizing solution at the temporary target temperature over the entire surface. D7) adding the treatment liquid to the sample; Supplying the first main surface of the test substrate and performing the predetermined treatment; d8) evaluating the state of the first main surface of the test substrate after the d7) step; and d9 ) If the state of the one main surface is good, the temporary target temperature is set as the target temperature, and if the state of the one main surface is not good, the state of the one main surface becomes good Until the temporary target temperature is lowered and the steps d5) to d8) are repeated to further determine the temporary target temperature when the state becomes good as the target temperature.

  The invention according to claim 25 is the substrate processing method according to claim 23 or 24, wherein the state of the one main surface is not good between the step d8) and the step d9). , D6) It further includes a step of changing the processing time of the step d6) to the step d8).

  The invention described in claim 26 is the substrate processing method according to any one of claims 15 to 19, wherein the step a) includes: a1) measuring a specific resistance of the charge removal solution; and a2) the step. a1) adjusting the temperature of the static elimination liquid so that the difference between the specific resistance of the static elimination liquid and a predetermined target specific resistance is reduced based on the measurement result in the step; a3) the a1) step and the a2 And a step of repeating the steps.

  A twenty-seventh aspect of the present invention is the substrate processing method according to any one of the fifteenth to nineteenth aspects, wherein the step a) includes: a1) measuring a specific resistance of the charge removal solution; and a2) the step. a1) Based on the measurement result in the step, when the difference between the specific resistance of the static elimination liquid and a predetermined target specific resistance is equal to or less than a threshold specific resistance difference, the specific resistance of the static elimination liquid is not adjusted without adjusting the temperature of the static elimination liquid. And adjusting the temperature of the static elimination liquid so that the difference between the specific resistance of the static elimination liquid and the target specific resistance is smaller when the difference between the specific resistance of the static elimination liquid and the target specific resistance is larger than the threshold specific resistance difference. Prepare.

  The invention according to claim 28 is the substrate processing method according to claim 26 or 27, wherein the smaller the size of the device formed in advance on the substrate, the larger the target specific resistance is set. Is done.

  A twenty-ninth aspect of the present invention is the substrate processing method according to any one of the fifteenth to twenty-eighth aspects, wherein the first main part of the substrate is interposed between the step b) and the step c). The method further includes a step of removing the static eliminating liquid from the surface.

  A thirty-third aspect of the present invention is the substrate processing method according to any one of the fifteenth to thirty-ninth aspects, wherein the neutralizing solution is pure water.

  A thirty-first aspect of the present invention is the substrate processing method according to any one of the fifteenth to thirtieth aspects, wherein the processing solution contains sulfuric acid.

  In the present invention, it is possible to prevent the substrate from being damaged due to the movement of charges during the treatment with the treatment liquid.

It is a figure which shows the structure of the substrate processing apparatus which concerns on 1st Embodiment. It is a figure which shows the structure of a single wafer processing apparatus. It is a figure which shows the relationship between the temperature of a pure water, and a specific resistance. It is a figure which shows the flow of a process of a board | substrate. It is a figure which shows a part of flow of a process of a board | substrate. It is a figure which shows a part of flow of a process of a board | substrate. It is a figure which shows the surface potential of the board | substrate before and behind a static elimination process. It is a figure which shows the flow of determination of target temperature. It is a figure which shows the flow of determination of target temperature. It is a figure which shows a part of flow of determination of target temperature. It is a figure which shows a part of flow of a process of a board | substrate. It is a figure which shows a part of flow of a process of a board | substrate. It is a figure which shows the structure of the substrate processing apparatus which concerns on 2nd Embodiment. It is a figure which shows the surface potential of the board | substrate before and behind a static elimination process. It is a figure which shows the structure of the substrate processing apparatus which concerns on 3rd Embodiment. It is a figure which shows a part of flow of a process of a board | substrate. It is a figure which shows the mode of the static elimination liquid on a board | substrate. It is a figure which shows the surface potential of the board | substrate before and behind a static elimination process.

  FIG. 1 is a diagram showing a configuration of a substrate processing apparatus 10 according to a first embodiment of the present invention. The substrate processing apparatus 10 is an apparatus for processing a semiconductor substrate 9 (hereinafter simply referred to as “substrate 9”). As shown in FIG. 1, the substrate processing apparatus 10 includes a single wafer processing apparatus 1, a charge removal liquid contact part 7, a temperature adjustment part 61, a charge removal liquid measurement part 62, and a control part 8.

  The single wafer processing apparatus 1 is a single wafer processing apparatus that processes the substrates 9 one by one. The static elimination liquid contact part 7 brings the substrate 9 into contact with the static elimination liquid. The temperature adjustment unit 61 adjusts the temperature of the static elimination liquid. The neutralization liquid measuring unit 62 is a temperature sensor that measures the temperature of the neutralization liquid. The storage unit 8a holds a target temperature and static elimination time (details will be described later), and sets them in the control unit 8 when executing substrate processing. The control unit 8 controls the configurations of the single wafer processing apparatus 1, the charge removal liquid contact unit 7, the temperature adjustment unit 61, the charge removal liquid measurement unit 62, and the like based on the target temperature and the like.

  FIG. 2 is a diagram illustrating a configuration of the single wafer processing apparatus 1. In the single wafer processing apparatus 1, an SPM (sulfuric acid / hydrogen peroxide mixture) liquid, which is a processing liquid, is supplied to the substrate 9 to perform an SPM process, that is, a resist film removal process on the substrate 9. The single wafer processing apparatus 1 includes a substrate holding unit 2, a processing liquid supply unit 3, a cup unit 41, and a substrate rotating mechanism 42. The substrate holding unit 2 holds the substrate 9 with one main surface 91 (hereinafter, referred to as “upper surface 91”) of the substrate 9 facing upward. The processing liquid supply unit 3 supplies a processing liquid such as an SPM liquid onto the upper surface 91 of the substrate 9. The cup part 41 surrounds the periphery of the substrate 9 and the substrate holding part 2. The substrate rotating mechanism 42 rotates the substrate 9 together with the substrate holding unit 2 horizontally. The substrate 9 is rotated about a rotation axis that passes through the center of the substrate 9 and is perpendicular to the upper surface 91 of the substrate 9 by the substrate rotation mechanism 42. In the single wafer processing apparatus 1, the substrate holding unit 2, the cup unit 41, the substrate rotating mechanism 42, and the like are accommodated in a chamber (not shown).

  The treatment liquid supply unit 3 generates a mixed liquid connected to the sulfuric acid supply unit 31 that supplies sulfuric acid, the hydrogen peroxide solution supply unit 32 that supplies hydrogen peroxide solution, the sulfuric acid supply unit 31, and the hydrogen peroxide solution supply unit 32. A processing liquid nozzle 34 that is disposed above the substrate 33 and that discharges liquid toward the substrate 9; and a processing liquid nozzle rotating mechanism 35 that rotates the processing liquid nozzle 34 horizontally around the rotation axis 351. Is provided. The processing liquid nozzle rotation mechanism 35 includes an arm 352 that extends in the horizontal direction from the rotation shaft 351 and to which the processing liquid nozzle 34 is attached.

  The sulfuric acid supply unit 31 is connected to the sulfuric acid storage unit 311 for storing sulfuric acid, the sulfuric acid storage unit 311 and the mixed liquid generation unit 33, and the sulfuric acid storage unit 311 to the mixed liquid generation unit 33 via the sulfuric acid piping 312. And a sulfuric acid pump 313 for supplying sulfuric acid, a sulfuric acid valve 314 provided on the sulfuric acid pipe 312, and a sulfuric acid heating unit 315 provided on the sulfuric acid pipe 312 between the sulfuric acid pump 313 and the sulfuric acid valve 314 for heating sulfuric acid. Prepare. The sulfuric acid pipe 312 branches between the sulfuric acid heating unit 315 and the sulfuric acid valve 314 and is connected to the sulfuric acid storage unit 311. When the sulfuric acid valve 314 is closed, the sulfuric acid heated by the sulfuric acid heating unit 315 is connected. Circulates between the sulfuric acid storage part 311 and the sulfuric acid heating part 315.

  The hydrogen peroxide solution supply unit 32 includes a hydrogen peroxide solution storage unit 321 for storing hydrogen peroxide solution, a hydrogen peroxide solution storage unit 321, and a hydrogen peroxide solution pipe 322 connected to the mixed solution generation unit 33. A hydrogen peroxide solution pump 323 for supplying hydrogen peroxide solution from the hydrogen water storage unit 321 to the mixed solution generating unit 33 through the hydrogen peroxide solution pipe 322, and a peroxide provided on the hydrogen peroxide solution tube 322 A hydrogen water valve 324 is provided. The sulfuric acid reservoir 311 and the hydrogen peroxide solution reservoir 321 may be provided outside the substrate processing apparatus 10, and the sulfuric acid pipe 312 and the hydrogen peroxide solution pipe 322 may be connected to each other.

  The mixed liquid generation unit 33 is provided on the mixing valve 331 to which the sulfuric acid pipe 312 and the hydrogen peroxide pipe 322 are connected, the discharge pipe 332 connected to the mixing valve 331 and the processing liquid nozzle 34, and the discharge pipe 332. A stirring flow pipe 333 is provided. In the mixed solution generation unit 33, the heated sulfuric acid from the sulfuric acid supply unit 31 and the hydrogen peroxide solution at room temperature (that is, a temperature similar to room temperature) from the hydrogen peroxide solution supply unit 32 are mixed with each other. Is mixed to produce an SPM liquid (sulfuric acid / hydrogen peroxide) as a mixed liquid.

  The SPM liquid passes through the stirring flow pipe 333 and the discharge pipe 332 and is sent to the processing liquid nozzle 34. In the stirring flow pipe 333, the chemical reaction between sulfuric acid and hydrogen peroxide contained in the SPM liquid is promoted by stirring the SPM liquid. The SPM liquid that is the processing liquid is discharged from the discharge port at the tip of the processing liquid nozzle 34 toward the upper surface 91 of the substrate 9. In the present embodiment, sulfuric acid heated to about 130 ° C. to 150 ° C. by the sulfuric acid heating unit 315 is supplied from the sulfuric acid supply unit 31 to the mixed liquid generation unit 33. Note that the temperature of the sulfuric acid supplied from the sulfuric acid supply unit 31 may be changed as appropriate.

  As shown in FIG. 1, the static elimination liquid contact part 7 holds the static elimination liquid storage part 71 that stores the static elimination liquid, the static elimination liquid supply part 72 that supplies the static elimination liquid to the static elimination liquid storage part 71, and a plurality of substrates 9. A cartridge 73 and a substrate drying unit 75 that performs a vacuum drying process on the substrate 9 are provided. In FIG. 1, illustration of a cartridge moving unit that holds and moves the cartridge 73 is omitted. In the static elimination liquid wetted part 7, pure water (DIW: deionized water) is used as the static elimination liquid.

FIG. 3 is a diagram showing the relationship between the temperature of pure water and the specific resistance. As shown in FIG. 3, the specific resistance of pure water gradually decreases as the liquid temperature increases. The specific resistance of pure water is greater than the specific resistance of the SPM liquid described above in the entire range from the freezing point of pure water to the boiling point. The neutralizing liquid used in the neutralizing liquid wetted part 7 is not limited to pure water as long as the specific resistance gradually decreases as the liquid temperature rises. In addition, the specific resistance of the static elimination liquid only needs to be larger than the specific resistance of the treatment liquid used in the single wafer processing apparatus 1 in at least a predetermined temperature range from the freezing point to the boiling point of the static elimination liquid. As the charge removal liquid, for example, a liquid containing ions such as CO ₂ water in which carbon dioxide (CO ₂ ) is dissolved in pure water may be used. The same applies to other embodiments.

  As shown in FIG. 1, the charge removal liquid supply unit 72 includes a charge removal liquid pipe 721, a flow meter 722, and a charge removal liquid valve 724. The neutralization liquid pipe 721 is connected to a neutralization liquid supply source (not shown). The static elimination liquid discharged from the tip of the static elimination liquid piping 721 is supplied to the static elimination liquid storage part 71 and stored therein. On the static elimination liquid pipe 721, a flow meter 722, a temperature adjustment unit 61, a static elimination liquid valve 724, and a static elimination liquid measuring unit 62 are sequentially arranged from the static elimination liquid supply source toward the static elimination liquid storage unit 71. The flow meter 722 measures the flow rate of the static elimination liquid flowing through the static elimination liquid pipe 721. The temperature adjustment unit 61 adjusts the temperature of the static elimination liquid in the static elimination liquid pipe 721 by heating or cooling the static elimination liquid flowing in the static elimination liquid pipe 721 as necessary. The neutralization liquid valve 724 adjusts the flow rate of the neutralization liquid flowing through the neutralization liquid pipe 721. The neutralization liquid measuring unit 62 measures the temperature of the neutralization liquid flowing in the neutralization liquid pipe 721.

  The measurement result of the neutralization liquid measuring unit 62 (that is, the temperature of the neutralization liquid) is sent to the control unit 8. Based on the target temperature of the neutralization liquid stored in the storage unit 8a, that is, the preferred temperature of the neutralization liquid in the neutralization process described later, the control unit 8 adjusts the temperature of the single wafer processing apparatus 1, the neutralization liquid wetted part 7, and the temperature adjustment. The configuration of the unit 61 and the neutralization liquid measuring unit 62 is controlled. The target temperature of the static elimination liquid is a temperature for realizing a preferable specific resistance (that is, a target specific resistance) of the static elimination liquid in the static elimination treatment. The target specific resistance of the static elimination liquid is larger than the specific resistance of the processing liquid used in the single wafer processing apparatus 1. The target temperature is obtained on the basis of the target specific resistance, the relationship between the temperature of the neutralizing liquid and the specific resistance shown in FIG. A specific method for obtaining the target temperature will be described later.

  The target specific resistance is set to be larger as the size of a device formed in advance on the upper surface 91 of the substrate 9 is smaller (that is, as the minimum width of the device wiring is smaller). Therefore, the target temperature is set to be lower as the size of the device formed in advance on the upper surface 91 of the substrate 9 is smaller. In the present embodiment, the target specific resistance is set in a range of about 1 to 18 MΩ · cm, and the target temperature is set in a range of about 25 to 100 ° C.

  In the substrate processing apparatus 10, the temperature adjustment unit 61 is feedback-controlled by the control unit 8 based on the measurement result of the static elimination liquid measuring unit 62 and the above-described target temperature. In the temperature adjustment unit 61, the temperature of the static elimination liquid is adjusted so that the difference between the temperature of the static elimination liquid in the static elimination liquid pipe 721 and the target temperature is small. Thereby, the temperature of the static elimination liquid supplied to the static elimination liquid storage part 71 is maintained at about target temperature. In other words, the above-described feedback control maintains the temperature of the static elimination liquid within a narrow temperature range (of course, including the target temperature) that can be said to be substantially equal to the target temperature.

  In the substrate processing apparatus 10, there are cases where the temperature of the static elimination liquid is allowed even if it is slightly deviated from the target temperature. In such a case, when the difference between the temperature of the static elimination liquid measured by the static elimination liquid measuring unit 62 and the target temperature is equal to or less than the threshold temperature difference, the temperature adjustment of the static elimination liquid by the temperature adjustment unit 61 is stopped by the control unit 8. Only when the difference between the temperature of the static elimination liquid and the target temperature is larger than the threshold temperature difference, the temperature adjustment unit 61 adjusts the temperature of the static elimination liquid. When the temperature lower than the target temperature by the threshold temperature difference is called “lower limit temperature” and the temperature higher than the target temperature by the threshold temperature difference is called “upper limit temperature”, the temperature is adjusted and supplied to the static elimination liquid storage unit 71. The temperature of the neutralizing liquid is approximately maintained within the range of the lower limit temperature and the upper limit temperature. The specific resistance of the static elimination liquid at the upper limit temperature is larger than the specific resistance of the processing liquid used in the single wafer processing apparatus 1.

  Thus, in the static elimination liquid supply part 72, when the control part 8 controls the temperature adjustment part 61, the temperature of static elimination liquid is made into the range in which the specific resistance of static elimination liquid becomes larger than the specific resistance of the said process liquid. To do.

  In the static elimination liquid contact part 7, the plurality of substrates 9 are held in a state in which the principal surfaces are arranged in parallel by the cartridge 73 disposed above the static elimination liquid storage part 71. Then, the cartridge 73 is lowered by the cartridge moving part, and the neutralizing liquid stored in the static eliminating liquid storage part 71 in a state in which the plurality of substrates 9 are arranged so that the normal direction of each main surface faces the horizontal direction. Soaked in.

  In the substrate drying unit 75, a reduced-pressure drying process is performed on the substrate 9 after being immersed in the charge removal solution. In the substrate drying unit 75, reduced-pressure drying processing may be performed on the plurality of substrates 9 held in the cartridge 73, and the substrates 9 removed from the cartridge 73 may be dried one by one. In the substrate drying unit 75, the drying process may be performed by various methods other than the vacuum drying process. The substrate 9 subjected to the vacuum drying process is carried into the single wafer processing apparatus 1. In FIG. 1, illustration of a transport mechanism for transporting the substrate 9 between the substrate drying unit 75 and the single wafer processing apparatus 1 is omitted.

  Next, the flow of processing of the substrate 9 in the substrate processing apparatus 10 will be described with reference to FIG. First, the target temperature and static elimination time corresponding to the substrate 9 to be used are read from the storage unit 8a and set in the control unit 8 (step S11). In this embodiment, the target temperature and the static elimination time are stored in advance in the storage unit 8a, and are read from the storage unit 8a and set in the control unit 8 when the substrate processing is started. However, the target temperature and the charge removal time may not be stored in the storage unit 8a, and the operator may set the control unit 8 using an input unit (not shown) every time substrate processing is started.

  Further, instead of storing the target temperature in the storage unit 8a, a table indicating the relationship between the size of the device on the substrate 9 and the target temperature of the charge removal liquid may be stored in the storage unit 8a in advance. In this case, before the substrate processing of the substrate 9 is started, the size of the device on the substrate 9 to be processed is input to the storage unit 8a, and then the substrate 9 is handled based on the size of the device and the table. The target temperature is determined, and finally, the target temperature is set in the control unit 8. The determination of the target temperature and static elimination time and the setting to the control unit 8 (or the determination and setting of the target specific resistance described later) are the same in other substrate processing apparatuses described later.

  Subsequently, the cartridge 73 holding the plurality of substrates 9 is carried into the substrate processing apparatus 10. Each substrate 9 is subjected to a dry process such as dry etching or plasma CVD (Chemical Vapor Deposition) before being carried into the substrate processing apparatus 10, and the substrate 9 is in a charged state.

  In the static elimination liquid contact part 7, the static elimination valve 724 is opened by the control unit 8 with the tip of the static elimination liquid pipe 721 facing away from the static elimination liquid storage part 71, and the static elimination liquid is discharged from the static elimination liquid pipe 721. (Pure water) discharge is started. Then, feedback control for the temperature adjustment unit 61 is performed based on the temperature of the neutralization solution, which is the measurement result of the neutralization solution measuring unit 62, and the above-described target temperature. Thereby, the temperature of the static elimination liquid is adjusted within a temperature range in which the specific resistance of the static elimination liquid is larger than the specific resistance of the treatment liquid (SPM liquid) used in the single wafer processing apparatus 1 (step S12).

  FIG. 5 is a diagram showing a flow of temperature adjustment (step S12) of the static elimination liquid. First, the temperature of the neutralizing liquid flowing through the neutralizing liquid pipe 721 is measured by the neutralizing liquid measuring unit 62 (step S121). Subsequently, based on the measurement result in step S121, the temperature adjustment unit 61 adjusts the temperature of the static elimination liquid so that the difference between the temperature of the static elimination liquid in the static elimination liquid pipe 721 and the target temperature becomes small (step S122). ). And step S121 and step S122 are repeated, and the temperature of a static elimination liquid is adjusted and maintained by about target temperature (step S123).

  As described above, in a case where the temperature of the static elimination liquid is allowed to be slightly deviated from the target temperature, temperature adjustment is performed as shown in FIG. 6 instead of steps S121 to S123 in FIG. First, the temperature of the static elimination liquid flowing through the static elimination liquid pipe 721 is measured by the static elimination liquid measuring unit 62 (step S124). Subsequently, based on the measurement result in step S124, the difference between the temperature of the static elimination liquid in the static elimination liquid piping 721 and the target temperature is obtained and compared with the above-described threshold temperature difference (step S125).

  When the difference between the temperature of the static elimination liquid and the target temperature is equal to or less than the threshold temperature difference, the temperature adjustment unit 61 does not adjust the temperature of the static elimination liquid. When the difference between the temperature of the static elimination liquid and the target temperature is larger than the threshold temperature difference, the temperature adjustment unit 61 adjusts the temperature of the static elimination liquid so that the difference between the temperature of the static elimination liquid and the target temperature becomes small (step) S126). Then, by repeating steps S124 to S126, the temperature of the static elimination liquid is within a temperature range not less than the lower limit temperature lower than the target temperature by a threshold temperature difference and not more than the upper limit temperature that is higher than the target temperature by the threshold temperature difference. Approximately adjusted and maintained.

  When the temperature adjustment of the static elimination liquid is completed, the tip of the static elimination liquid pipe 721 is directed to the static elimination liquid storage part 71, and the static elimination liquid is supplied from the static elimination liquid supply part 72 to the static elimination liquid storage part 71 and stored. (Step S13). The neutralization liquid wetted part 7 further includes an auxiliary measurement unit that measures the temperature of the neutralization liquid in the neutralization liquid storage part 71 and an auxiliary adjustment unit that adjusts the temperature of the neutralization liquid in the neutralization liquid storage part 71. Also good. In this case, the auxiliary adjusting unit is controlled on the basis of the measurement result of the auxiliary measuring unit, and the neutralizing liquid as necessary so that the neutralizing liquid in the neutralizing liquid storage unit 71 has a desired temperature (for example, a target temperature). Is heated or cooled by the auxiliary adjustment unit.

  Thereafter, the cartridge moving unit is controlled by the control unit 8, and the cartridge 73 disposed above the static elimination liquid storage unit 71 is lowered toward the static elimination liquid storage unit 71. Then, the plurality of substrates 9 held by the cartridge 73 are immersed in the charge removal liquid in the charge removal liquid storage section 71. Each substrate 9 is gradually immersed in the charge removal liquid from the lower part of the edge held in the cartridge 73, and the whole substrate 9 is immersed, so that the main surfaces on both sides of the substrate 9 are entirely covered. To touch. Further, the static elimination liquid that contacts the main surfaces on both sides of the substrate 9 continues on the edge of the substrate 9.

  In the substrate 9, when the main surface on which the device is provided is referred to as a “first main surface” and the other main surface is referred to as a “second main surface”, the substrate 9 is immersed in the charge removal solution. The first main surface and the second main surface are in contact with the charge removal solution over the entire surface. The static elimination liquid that contacts the first main surface is continuous with the static elimination liquid that contacts the second main surface on the edge of the substrate 9. In this way, when the substrate 9 comes into contact with the charge removal solution, the charges on the substrate 9 move relatively slowly to the charge removal solution. In the substrate processing apparatus 10, since the liquid contact state of the substrate 9 with respect to the charge removal liquid is maintained for a predetermined time, the charge on the substrate 9 is reduced without damaging the devices on the substrate 9. In other words, the charge removal process is performed on the substrate 9 (step S14).

  FIG. 7 is a diagram illustrating the surface potential of the upper surface 91 of the substrate 9 before and after the charge removal process by the substrate processing apparatus 10. FIG. 7 shows the absolute value of the surface potential at the center of the substrate 9 (the same applies to FIGS. 13 and 17). By the above-described charge removal process, the charge on the substrate 9 is reduced, and the potential of the substrate 9 is reduced as a whole. In the substrate processing apparatus 10, when the size of the device on the substrate 9 is relatively small, the temperature of the static elimination liquid is maintained at about 25 ° C., for example, and the specific resistance of the static elimination liquid is about 18 MΩ · cm. Further, when the size of the device on the substrate 9 is relatively large (that is, the resistance against damage due to the movement of electric charges is relatively high), the temperature of the static elimination liquid is maintained at a temperature slightly lower than, for example, 100 ° C. The specific resistance is about 1 MΩ · cm. In this way, by increasing the temperature of the neutralization solution and making the specific resistance relatively small, the movement speed of charges from the substrate 9 to the neutralization solution increases. As a result, the time required for the charge removal process of the substrate 9 can be shortened.

  When the neutralization process of the substrate 9 is completed, the substrate drying unit 75 controlled by the control unit 8 performs a decompression drying process on the substrate 9 to remove the neutralization liquid from the entire upper surface 91 and the entire lower surface 92 of the substrate 9 ( Step S15). In other words, the substrate drying unit 75 is a liquid discharger supplying unit 72 that removes liquid on the upper surface 91 and the lower surface 92 of the substrate 9. Subsequently, one substrate 9 is carried into the single wafer processing apparatus 1 shown in FIG. 2, and is held by the substrate holding unit 2 with the upper surface 91 facing upward. Next, the substrate rotating mechanism 42 is controlled by the control unit 8 to start the rotation of the substrate 9 (step S16). Also, the processing liquid nozzle rotating mechanism 35 starts to rotate the processing liquid nozzle 34, and the processing liquid nozzle 34 repeats reciprocating motion between the center portion and the edge of the substrate 9.

  Next, when the processing liquid supply unit 3 is controlled by the control unit 8, the sulfuric acid valve 314 of the sulfuric acid supply unit 31 is opened, and the sulfuric acid heated to about 130 ° C. to 150 ° C. by the sulfuric acid heating unit 315 is converted into sulfuric acid. The mixture is supplied to the mixing valve 331 of the mixed liquid generation unit 33 via the pipe 312. Further, the control unit 8 opens the hydrogen peroxide solution valve 324, and normal temperature hydrogen peroxide solution is supplied from the hydrogen peroxide solution storage unit 321 to the mixing valve 331 via the hydrogen peroxide solution pipe 322. In the mixing valve 331, the heated sulfuric acid and the hydrogen peroxide solution at room temperature are mixed to generate the SPM liquid. The temperature of the SPM solution is about 150 ° C. to 195 ° C., which is higher than the temperature of sulfuric acid supplied from the sulfuric acid supply unit 31 due to the reaction between sulfuric acid and hydrogen peroxide.

  The SPM liquid passes through the discharge pipe 332 and the stirring flow pipe 333 and is supplied from the processing liquid nozzle 34 to the upper surface 91 of the substrate 9. In other words, heated sulfuric acid and hydrogen peroxide solution are mixed and supplied to the upper surface 91 of the substrate 9 by the processing liquid supply unit 3. The SPM liquid spreads over the entire upper surface 91 of the substrate 9 by the rotation of the substrate 9, scatters from the edge of the substrate 9 to the outside, and is received by the cup portion 41. In the single wafer processing apparatus 1, the supply of the SPM liquid to the substrate 9 is continuously performed for a predetermined time, and the resist film on the substrate 9 due to the SPM process for the substrate 9, that is, the strong oxidizing power of caloic acid contained in the SPM liquid. Is removed (step S17). In the single wafer processing apparatus 1, the SPM liquid or the like may be supplied from the processing liquid nozzle 34 stopped above the center of the substrate 9.

  When the SPM treatment is completed, the sulfuric acid valve 314 is closed with the hydrogen peroxide solution valve 324 opened, and the hydrogen peroxide solution passes through the mixing valve 331, the discharge pipe 332, and the stirring flow pipe 333, and the treatment liquid From the nozzle 34, the resist film is supplied onto the substrate 9 (step S18). By the hydrogen peroxide supply process, the SPM liquid remaining in the mixing valve 331, the discharge pipe 332, the stirring flow pipe 333, and the processing liquid nozzle 34 is removed. Further, the hydrogen peroxide solution supplied onto the substrate 9 spreads over the entire upper surface 91 of the substrate 9 by the rotation of the substrate 9, and the SPM liquid remaining on the substrate 9 is moved outward from the edge of the substrate 9. Extrude and remove.

When the hydrogen peroxide solution supply process is completed, the hydrogen peroxide solution valve 324 is closed and the supply of the hydrogen peroxide solution is stopped, and the treatment solution nozzle 34 is placed on standby outside the substrate 9 by the treatment solution nozzle rotating mechanism 35. Moved to position. Next, a rinsing process is performed in which a rinsing liquid is supplied from an unillustrated rinsing liquid supply unit to the upper surface 91 of the substrate 9 (step S19). As the rinse liquid, for example, pure water or CO ₂ water is used. The rinse liquid spreads over the entire upper surface 91 of the substrate 9 by the rotation of the substrate 9. Thereby, the hydrogen peroxide remaining on the substrate 9 is washed away. When the rinsing process is continuously performed for a predetermined time, the supply of the rinsing liquid is stopped. Then, the number of rotations of the substrate 9 is increased, and a drying process is performed to remove the rinse liquid remaining on the substrate 9 by the rotation of the substrate 9 (step S20). Thereafter, the rotation of the substrate 9 is stopped (step S21), and the substrate 9 is unloaded from the substrate processing apparatus 10.

  As described above, in the substrate processing apparatus 10, the substrate 9 that has been charged by the pretreatment such as dry etching or plasma CVD is processed with the processing liquid in the single wafer processing apparatus 1 (that is, the SPM processing with the SPM liquid). ), The main surface on both sides of the substrate 9 is brought into contact with the charge-removing solution having a higher specific resistance than that of the processing solution over the entire surface to maintain the liquid contact state. As a result, the entire main surface on both sides of the substrate 9 is discharged relatively slowly. At the time of static elimination, the charges on the substrate 9 do not suddenly move to the static elimination liquid and do not generate heat, so that damage to the device on the substrate 9 is prevented.

  Then, even if the substrate 9 comes into contact with the treatment liquid having a specific resistance smaller than that of the charge removal liquid by supplying the treatment liquid to the substrate 9 after the charge removal process, the treatment is performed from the substrate 9. A large amount of charge does not move rapidly into the liquid. For this reason, also in the process by the process liquid in the single wafer processing apparatus 1, the damage of the device by the movement of electric charges, that is, the damage of the substrate 9 can be prevented.

  In the substrate processing apparatus 10, by adjusting the temperature of the static elimination liquid by the temperature adjustment unit 61, the specific resistance of the static elimination liquid is maintained in a state larger than the specific resistance of the treatment liquid used in the single wafer processing apparatus 1. Meanwhile, the main surface on both sides of the substrate 9 is brought into contact with the charge eliminating liquid. As a result, as described above, it is possible to perform the charge removal process on the substrate 9 without damaging the device. Further, by increasing the temperature of the neutralization solution and decreasing the specific resistance within a range that does not damage the device, the charge transfer rate from the substrate 9 to the neutralization solution can be increased. As a result, the time required for the charge removal process of the substrate 9 can be shortened.

The specific resistance of the static elimination liquid can be adjusted, for example, by using a liquid containing ions obtained by dissolving carbon dioxide (CO ₂ ) or the like in pure water as the static elimination liquid and adjusting the ion concentration of the static elimination liquid. . However, since this method uses carbon dioxide or the like, the cost required for the charge removal process may increase. In addition, the specific resistance of the static elimination liquid cannot be increased as compared with pure water at the same temperature. On the other hand, in the substrate processing apparatus 10 described above, the specific resistance of the static elimination liquid is adjusted by adjusting the temperature of the static elimination liquid. Therefore, the specific resistance of the static elimination liquid can be easily adjusted at low cost. it can.

  As described above, in the substrate processing apparatus 10, the smaller the device size on the substrate 9, the lower the temperature is determined as the target temperature of the static elimination liquid, and the higher specific resistance is determined as the target specific resistance. Thereby, it is possible to appropriately perform both the prevention of damage to the substrate 9 during processing in the single wafer processing apparatus 1 and the reduction of the time required for the static elimination processing in accordance with the size of the device.

  In the static elimination liquid contact part 7, the static elimination liquid that contacts one main surface of the substrate 9 and the static elimination liquid that contacts the other main surface are continuous on the edge of the substrate 9. As a result, the surface potential (absolute value) of the substrate 9 can be reduced by the neutralization process as compared with the case where the neutralization liquid in contact with one main surface of the substrate 9 and the neutralization solution in contact with the other main surface are not continuous. , Can be smaller.

  In the static elimination liquid contact part 7, the whole of the substrate 9 is immersed in the static elimination liquid, so that the static elimination liquid in contact with one main surface of the substrate 9 and the static elimination liquid in contact with the other main surface are easily continued. Can do. In addition, since the amount of the neutralizing liquid that contacts the unit area of the substrate 9 can be easily increased, the surface potential (absolute value) of the substrate 9 can be further reduced.

  As described above, in the static elimination liquid contact part 7, the plurality of substrates 9 are immersed in the static elimination liquid in the static elimination liquid storage part 71 at a time, so that the static elimination treatment of the plurality of substrates 9 can be performed efficiently. In addition, since it is not necessary to frequently supply the neutralization liquid to the neutralization liquid reservoir 71, it is possible to suppress the generation of electric charges in the neutralization liquid due to friction between the neutralization liquid and the neutralization liquid pipe 721. Furthermore, since each substrate 9 is gradually immersed from the edge, even if the substrate 9 is damaged due to the movement of electric charge from the substrate 9 to the charge removal liquid, the influence on the devices on the substrate 9 is small. Damage occurs only in the vicinity of the edge of the substrate 9. For this reason, the yield of devices can be improved.

  In the static elimination liquid contact part 7, the temperature of the static elimination liquid can be accurately adjusted by performing the temperature adjustment shown in the above steps S121 to S123. Moreover, when the temperature adjustment shown to step S124-S126 is performed, control of the temperature adjustment part 61 by the control part 8 can be simplified compared with the case where the temperature adjustment shown to step S121-S123 is performed.

As described above, in the static elimination liquid wetted part 7, pure water is used as the static elimination liquid. Thus, as anti-static liquid, as compared with the case of using a liquid containing pure water were dissolved carbon dioxide (CO ₂₎ and ion, it is possible to reduce the cost of the use of anti-static liquid.

  In the substrate processing apparatus 10, the charge removal liquid on the substrate 9 is removed by the drying process in step S <b> 15 between the charge removal process in step S <b> 14 and the process using the process liquid in step S <b> 17 (SPM process). Thereby, the bad influence by mixing of the static elimination liquid and processing liquid on the board | substrate 9 can be prevented. The adverse effects include, for example, damage to the substrate 9 due to the reaction heat between pure water as a static elimination liquid and sulfuric acid contained in the SPM liquid (so-called heat shock), and SPM treatment due to dilution of the SPM liquid with the static elimination liquid. For example, the concentration of the SPM liquid becomes non-uniform due to the deterioration of the quality and the partial mixing of the SPM liquid with the charge eliminating liquid, and the uniformity of the SPM treatment in the entire substrate 9 is reduced.

  FIG. A and FIG. B is a diagram illustrating an example of a flow of determining a target temperature set in the control unit 8 in step S11 in FIG. In the target temperature determination process, first, the specific resistance of the processing liquid (SPM liquid) to be used in step S17 is measured and obtained (step S611). Subsequently, the relationship between the temperature of the static eliminating liquid (pure water) shown in FIG. 3 and the specific resistance is also acquired (step S612). Then, based on the relationship obtained in step S612, the temperature of the static elimination liquid at which the specific resistance of the static elimination liquid becomes equal to the specific resistance of the treatment liquid is acquired (step S613).

  Next, a temporary target temperature slightly lower than the temperature acquired in step S613 is set, and a static elimination liquid having the temporary target temperature is prepared (steps S614 and S615). In parallel with the preparation of the charge removal liquid, a test substrate having the same structure as the substrate 9 is prepared. The test substrate is immersed in a static elimination liquid having a temporary target temperature stored in the storage unit. As a result, the main surfaces on both sides of the test substrate are in contact with the neutralization solution over the entire surface, and the liquid contact state is maintained for a predetermined time, whereby the charge on the test substrate is reduced. In other words, the charge removal process is performed on the test substrate (step S616).

  When the neutralization process is completed, the test substrate is taken out of the neutralization solution and dried, whereby the neutralization solution is removed from both surfaces of the test substrate. Subsequently, the processing liquid is supplied onto the upper surface of the test substrate (that is, the surface on which the device is formed in advance), and a predetermined process (SPM process) is performed as in step S17 (step S617).

  When the SPM process is completed, the state of the upper surface of the test substrate is evaluated by being observed (step S618). If the state of the upper surface is good (step S619), the temporary target temperature is determined as the target temperature. . The target temperature is stored in the storage unit 8a (step S623). In step S619, when the device on the upper surface is not damaged in the test substrate, it is evaluated that the state of the upper surface is good, and when the device is damaged, it is evaluated that the state of the upper surface is not good. Is done.

  When the state of the upper surface of the test substrate is not good (step S619), the time for the charge removal process in step S616 (that is, the time for maintaining the liquid contact state with respect to the charge removal solution of the test substrate) is changed to be long, A static elimination process is performed on a new test substrate (steps S620, S621, and S616). Then, the SPM process and the evaluation of the state of the upper surface of the test substrate are performed (steps S617 and S618). The static elimination process, the SPM process, and the evaluation of the test substrate with the static elimination process time changed are repeated a predetermined number of times (steps S619 to S621). However, if it is determined in step S619 that the state of the upper surface of the test substrate is good before the predetermined number of repetitions is completed, the temporary target temperature is determined as the target temperature, and the charge removal process in the latest step S616 is performed. Is determined as the static elimination time in step S14. The static elimination time is stored in the storage unit 8a. (Step S623).

  On the other hand, if it is not determined that the state of the upper surface of the test substrate is good even after the predetermined number of repetitions, the temporary target temperature is lowered (steps S619, S620, S622). In other words, a temperature lower than the latest temporary target temperature is set as the temporary target temperature. And the static elimination process with respect to a new test board | substrate, SPM process, and the evaluation of a test board | substrate are performed (step S616-S618). If the state of the upper surface of the test substrate becomes good, the temporary target temperature is determined as the target temperature (steps S619 and S623). If the state of the upper surface of the test substrate is not good, the static elimination time is changed longer (steps S619 to S621), and the static elimination process, the SPM process, and the evaluation of the test substrate are repeated a predetermined number of times (steps S616 to S616). S621).

  As described above, by repeating Steps S616 to S622, the temporary target temperature and the static elimination time at which the state of the upper surface of the test substrate after the SPM processing becomes favorable are determined as the target temperature and the static elimination time (Step S623). . And in the substrate processing apparatus 10, by performing the static elimination process using the static elimination liquid of the said target temperature, the damage of the board | substrate 9 can be prevented in the process by a process liquid. Further, by performing the static elimination process for the set static elimination time, it is possible to prevent the static elimination time from being excessively increased.

  In this target static elimination temperature determination process, a temperature slightly lower than the temperature of the static elimination liquid at which the specific resistance is equal to the treatment liquid is set as a temporary target temperature at the start of the target static elimination temperature acquisition process (step S614). The target temperature is gradually lowered (step S622), and the temporary target temperature at the time when the upper surface of the test substrate becomes satisfactory is set as the final target temperature (step S622). The higher the temperature of the charge removal solution, the shorter the charge removal time. Therefore, the temperature at which the charge removal time is the shortest in the temperature range that does not damage the upper surface of the test substrate is determined as the final target temperature. be able to.

  FIG. 9 is a diagram illustrating another example of determining the target temperature. FIG. 9 shows a part of the flow for determining the target temperature. First, the specific resistance of the processing liquid (SPM liquid) to be used in step S17 is measured and obtained (step S631). Subsequently, a specific resistance slightly higher than the specific resistance of the processing liquid is set as the temporary target specific resistance (step S632). Moreover, the relationship between the temperature of the static elimination liquid (pure water) shown in FIG. 3 and specific resistance is also acquired (step S633). Based on the relationship obtained in step S633, the temperature of the static elimination liquid at which the specific resistance of the static elimination liquid becomes equal to the specific resistance set in step S632 is acquired as a temporary target temperature (step S634).

  Thereafter, the same processes as those in steps S615 to S623 described above are performed, and the temporary target temperature and the static elimination time at which the state of the upper surface of the test substrate after the SPM process is good are determined as the target temperature and the static elimination time. And in the substrate processing apparatus 10, by performing the static elimination process using the static elimination liquid of the said target temperature, the damage of the board | substrate 9 can be prevented in the process by a process liquid. Further, by performing the static elimination process for the set static elimination time, it is possible to prevent the static elimination time from being excessively increased. FIG. A, FIG. The target temperature determination process shown in B and FIG. 9 may be performed in the substrate processing apparatus 10 or may be performed without using the substrate processing apparatus 10.

  In the substrate processing apparatus 10 illustrated in FIG. 1, a specific resistance meter may be used as the static elimination liquid measuring unit 62, and the specific resistance of the static elimination liquid may be measured by the static elimination liquid measuring unit 62. In this case, in the substrate processing apparatus 10, instead of step S <b> 11 shown in FIG. 4, as shown in FIG. 10, a target specific resistance that is a preferable specific resistance of the charge removal solution in the charge removal process is set in the control unit 8 ( Step S31). Further, the relationship between the temperature of the neutralizing solution and the specific resistance as shown in FIG.

  Subsequently, in place of steps S121 to S123 shown in FIG. 5, the specific resistance of the neutralizing liquid flowing in the neutralizing liquid pipe 721 is measured by the neutralizing liquid measuring unit 62 (step S321). Next, based on the measurement result in step S321 and the relationship between the temperature of the neutralizing liquid and the specific resistance, the temperature is set so that the difference between the specific resistance of the neutralizing liquid in the neutralizing liquid pipe 721 and the target specific resistance becomes small. The temperature of the static elimination liquid is adjusted by the adjustment unit 61 (step S322). And by repeating step S321 and step S322, the specific resistance of a static elimination liquid is adjusted and maintained by the target specific resistance (step S323). Thereby, the specific resistance of a static elimination liquid can be adjusted accurately.

  In a case where the specific resistance of the charge removal liquid is allowed to be slightly deviated from the target specific resistance, temperature adjustment is performed as shown in FIG. 11 instead of steps S321 to S323 in FIG. First, the specific resistance of the neutralizing liquid flowing through the neutralizing liquid pipe 721 is measured by the neutralizing liquid measuring unit 62 (step S324). Subsequently, based on the measurement result in step S324, the difference between the specific resistance of the static elimination liquid in the static elimination liquid pipe 721 and the target specific resistance is obtained and compared with a predetermined threshold specific resistance difference (step). S325).

  When the difference between the specific resistance of the static elimination liquid and the target specific resistance is not more than the threshold specific resistance difference, the temperature adjustment unit 61 does not adjust the temperature of the static elimination liquid. When the difference between the specific resistance of the static elimination liquid and the target specific resistance is larger than the threshold specific resistance difference, the temperature adjustment unit 61 adjusts the temperature of the static elimination liquid so that the difference between the specific resistance of the static elimination liquid and the target specific resistance becomes small. Adjustment is made (step S326). When a specific resistance that is smaller than the target specific resistance by the threshold specific resistance is called a “lower limit specific resistance” and a specific resistance that is larger than the target specific resistance by the threshold specific resistance is called an “upper limit specific resistance”, steps S324 to S326 are performed. By being repeated, the specific resistance of the static elimination liquid is adjusted and maintained within the range of the lower limit specific resistance and the upper limit specific resistance. Thereby, compared with the case where the temperature adjustment shown to step S321-S323 is performed, control of the temperature adjustment part 61 by the control part 8 can be simplified.

  In the substrate processing apparatus 10, when the above-described steps S <b> 31 and S <b> 321 to S <b> 323 are performed, the target specific resistance of the static elimination liquid is set to be larger as the device size on the substrate 9 is smaller. Thereby, it is possible to appropriately perform both the prevention of damage to the substrate 9 during processing in the single wafer processing apparatus 1 and the reduction of the time required for the static elimination processing in accordance with the size of the device. The same applies when steps S31 and S324 to S326 are performed.

  Next, a substrate processing apparatus 10a according to a second embodiment of the present invention will be described. FIG. 12 is a diagram showing a configuration of the substrate processing apparatus 10a. In the substrate processing apparatus 10a, the static elimination liquid contact part 7 is provided with a static elimination liquid storage part 71a smaller than the static elimination liquid storage part 71 shown in FIG. One substrate 9 is immersed in the charge removal liquid stored in the charge removal liquid storage section 71a. In the substrate processing apparatus 10a, the cartridge 73 and the like shown in FIG. 1 are omitted. Other configurations are the same as those of the substrate processing apparatus 10 shown in FIG. 1, and the same reference numerals are given to the corresponding configurations in the following description.

  The flow of the substrate processing in the substrate processing apparatus 10a is substantially the same as that shown in FIG. 4, and when the substrate 9 is immersed in the charge removal liquid in the charge removal liquid storage section 71a under the control of the control section 8 in step S14. The only difference is that one substrate 9 is immersed from a main surface opposite to the upper surface 91 (hereinafter referred to as “lower surface 92”).

  FIG. 13 is a diagram showing the surface potential of the upper surface 91 of the substrate 9 before and after the charge removal process by the substrate processing apparatus 10a. By the above-described charge removal process, the charge on the substrate 9 is reduced, and the potential of the substrate 9 is reduced as a whole. As a result, similarly to the substrate processing apparatus 10 shown in FIG. 1, device damage due to the movement of charges, that is, the substrate 9 during the SPM process in the single wafer processing apparatus 1 for the substrate 9 after the charge removal process is performed. Can prevent damage. Further, in the static elimination liquid contact portion 7, the static elimination liquid that contacts the upper surface 91 and the lower surface 92 of the substrate 9 is continuous on the edge of the substrate 9. Thereby, the surface potential (absolute value) of the substrate 9 can be further reduced by the charge removal process. Furthermore, in the static elimination liquid wetted part 7, the surface potential (absolute value) of the substrate 9 can be further reduced by immersing the entire substrate 9 in the static elimination liquid.

  Next, a substrate processing apparatus 10b according to a third embodiment of the present invention will be described. FIG. 14 is a diagram showing the configuration of the substrate processing apparatus 10b. In the substrate processing apparatus 10b, instead of the static elimination liquid wetted part 7, the single wafer processing apparatus 1 is provided with the static elimination liquid wetted part 7a. In the static elimination liquid contact part 7a, a static elimination liquid storage part, a board | substrate drying part, etc. are not provided, but the static elimination liquid supply part 72a from which the static elimination liquid supply part 72 shown in FIG. Other configurations are the same as those of the substrate processing apparatus 10 shown in FIG. 1, and the same reference numerals are given to the corresponding configurations in the following description.

  As in the case of the neutralization liquid supply unit 72 shown in FIG. 1, the neutralization liquid supply unit 72a includes a neutralization liquid pipe 721, a flow meter 722, and a neutralization liquid valve 724. It is connected to the omitted neutralizer supply source. The neutralization liquid supply unit 72 a includes a neutralization liquid nozzle 725 provided at the tip of the neutralization liquid pipe 721, and a neutralization liquid nozzle rotation mechanism 728 that rotates the neutralization liquid nozzle 725 horizontally around the rotation axis 7281. The neutralization liquid nozzle rotation mechanism 728 includes an arm 7282 that extends in the horizontal direction from the rotation shaft 7281 and to which the neutralization liquid nozzle 725 is attached. On the static elimination liquid pipe 721, a flow meter 722, a temperature adjustment unit 61, a static elimination liquid valve 724, and a static elimination liquid measurement unit 62 are sequentially arranged from the static elimination liquid supply source toward the static elimination liquid nozzle 725.

  In the single wafer processing apparatus 1, a part of the outer edge portion of the substrate 9 is supported by the substrate holding unit 2, and the lower surface 92 of the substrate 9 and the substrate holding unit 2 are excluded except for the part that comes into contact with the substrate holding unit 2. Are separated. The neutralization liquid supply unit 72 a further includes a lower surface liquid contact part 761 that supplies the neutralization liquid to the lower surface 92 of the substrate 9. The lower surface liquid contact portion 761 is disposed at a position facing the center portion of the lower surface 92 of the substrate 9, and discharges the neutralizing liquid toward the lower surface 92. The lower surface wetted part 761 is connected to the static elimination liquid pipe 721 via the lower surface pipe 762, and a lower surface valve 763 is provided on the lower surface pipe 762.

  In the static elimination liquid wetted part 7a, the temperature adjustment unit 61 is controlled by the control part 8 in which the target temperature is set, as in the static neutralizing liquid wetted part 7, thereby adjusting the temperature of the static elimination liquid (FIG. 4: Steps S11 and S12) are maintained at approximately the target temperature. Thereby, the specific resistance of the static elimination liquid is maintained at a target specific resistance. Or the temperature of a static elimination liquid may be maintained approximately in the range below the upper limit temperature and below the upper limit temperature. In the static elimination liquid contact part 7a, as shown in FIG. 10 or FIG. 11, a target specific resistance is set in the control unit 8 (step S31), and the temperature of the static elimination liquid may be adjusted based on the target specific resistance ( Steps S321 to S323 or Steps S324 to S326).

  The neutralized liquid whose temperature has been adjusted is sent to the neutralizing liquid nozzle 725 and the lower surface wetted part 761, and the upper surface of the substrate 9 is ejected from the discharge port at the tip of the neutralizing liquid nozzle 725 directed to the upper part of the upper surface 91 of the substrate 9. A static elimination liquid is supplied to 91, and a static elimination liquid is supplied to the lower surface 92 of the substrate 9 from a lower surface wetted portion 761 facing the center of the lower surface 92 of the substrate 9. When the static elimination liquid nozzle 725 and the lower surface wetted part 761 are respectively referred to as a first static elimination liquid wetted part and a second static elimination liquid wetted part, in the static elimination liquid wetted part 7a, the first static elimination liquid wetted part and the second static elimination liquid wetted part, respectively. Due to the liquid contact portion, the upper surface 91 and the lower surface 92 of the substrate 9 come into contact with the static elimination liquid.

  FIG. 15 is a diagram showing a part of the processing flow of the substrate 9 in the substrate processing apparatus 10b. First, similarly to the substrate processing apparatus 10 shown in FIG. 1, the target temperature of the static elimination liquid determined based on the size of the device on the substrate 9 is set in the control unit 8 (step S41). Subsequently, the charged substrate 9 is carried into the substrate processing apparatus 10 b and is held by the substrate holding unit 2 of the single wafer processing apparatus 1.

  In the neutralization liquid wetted part 7a, discharge of the neutralization liquid (pure water) from the neutralization liquid nozzle 725 is started in a state where the neutralization liquid nozzle 725 is positioned at the standby position outside the substrate 9. Then, feedback control for the temperature adjustment unit 61 is performed based on the temperature of the neutralization solution, which is the measurement result of the neutralization solution measuring unit 62, and the above-described target temperature. Thereby, the temperature of the static elimination liquid is adjusted within a temperature range in which the specific resistance of the static elimination liquid is larger than the specific resistance of the treatment liquid (SPM liquid) (step S42). The details of the temperature adjustment of the static elimination liquid are the same as steps S121 to S123 in FIG. 5 or steps S124 to S126 in FIG.

  When the temperature adjustment of the neutralizing liquid is completed, the substrate 9 starts rotating by the substrate rotating mechanism 42 shown in FIG. Subsequently, as shown in FIG. 16, the lower surface valve 763 is opened, and the discharge liquid 95 whose temperature is adjusted as described above from the discharge port at the tip of the lower surface wetted part 761 toward the lower surface 92 of the substrate 9. Discharge is started. The rotation speed of the substrate 9 is lower than the rotation speed during the SPM process described later. The neutralizing liquid 95 that has come into contact with the lower surface 92 of the substrate 9 spreads from the central portion of the lower surface 92 of the substrate 9 to the entire surface by the rotation of the substrate 9. When the static elimination liquid 95 spreads over the entire lower surface 92 of the substrate 9, the discharge of the static elimination liquid 95 and the rotation of the substrate 9 are stopped. As a result, the state in which the entire lower surface 92 of the substrate 9 (excluding the contact portion with the substrate holding unit 2) is in contact with the charge removal liquid 95 is maintained, and as a result, the charge on the lower surface 92 of the substrate 9 is reduced. It moves relatively slowly to 95, and the charge removal process is performed on the entire lower surface 92 of the substrate 9 (step S43).

  When the supply of the neutralization liquid 95 to the lower surface 92 of the substrate 9 is completed, the neutralization liquid nozzle 725 is moved from the standby position by the neutralization liquid nozzle rotating mechanism 728, and the discharge port at the tip of the neutralization liquid nozzle 725 is moved to the upper surface of the substrate 9. It faces the center of 91. Then, after a predetermined amount of the neutralizing liquid 95 is supplied from the neutralizing liquid nozzle 725 onto the upper surface 91 of the substrate 9, the supply of the neutralizing liquid 95 from the neutralizing liquid nozzle 725 is stopped (so-called liquid accumulation is performed). .) The neutralizing liquid 95 supplied from the neutralizing liquid nozzle 725 spreads from the center of the substrate 9 to the entire upper surface 91, and a thin layer (for example, a layer having a thickness of about 1 mm) of the neutralizing liquid 95 is formed on the upper surface 91. The whole 91 is paddled with the charge removal liquid 95 (step S44). As a result, the charge on the upper surface 91 of the substrate 9 moves relatively slowly to the charge removal liquid 95, and the charge removal process for the entire upper surface 91 of the substrate 9 is performed. It should be noted that the neutralizing liquid 95 that is in contact with the lower surface 92 of the substrate 9 and the neutralizing liquid 95 that is in contact with the upper surface 91 of the substrate 9 are not continuous on the substrate 9.

  In the substrate processing apparatus 10b, in a state where the substrate rotating mechanism 42 is stopped, the entire upper surface 91 of the substrate 9 is padded with the neutralizing liquid 95, and the entire lower surface 92 of the substrate 9 is in contact with the neutralizing liquid 95. By maintaining for a predetermined time, the charge removal process is performed on the entire upper surface 91 and the entire lower surface 92 of the substrate 9.

  When the neutralization process is completed, the rotation of the substrate 9 is started (FIG. 4: step S16), and the neutralizing liquid on the upper surface 91 and the lower surface 92 of the substrate 9 is removed by the rotation of the substrate 9. This prevents the charge-removing solution and the SPM solution from being mixed on the upper surface 91 of the substrate 9 during the next SPM process. As a result, it is possible to prevent the above-described adverse effects due to the mixing of the charge removal liquid and the treatment liquid on the substrate 9.

  When the removal of the static elimination liquid is completed, the SPM liquid is supplied onto the upper surface 91 of the substrate 9 from the processing liquid supply unit 3 shown in FIG. 14 and the SPM process is performed (step S17). Subsequently, after the hydrogen peroxide solution is supplied from the treatment liquid supply unit 3 onto the upper surface 91 of the substrate 9 and the hydrogen peroxide solution supply process is performed, the rinse solution (pure water) is applied onto the upper surface 91 of the substrate 9. The supplied rinse process is performed (steps S18 and S19). The rinsing liquid may be supplied from a rinsing liquid supply unit (not shown) or may be supplied from the static elimination liquid nozzle 725 of the static elimination liquid contact part 7a. Thereafter, a drying process for removing the rinse liquid on the substrate 9 is performed by the rotation of the substrate 9, and the rotation of the substrate 9 is stopped (steps S20 and S21).

  FIG. 17 is a diagram illustrating the surface potential of the upper surface 91 of the substrate 9 before and after the charge removal process by the substrate processing apparatus 10b. By the above-described charge removal process, the charge on the substrate 9 is reduced, and the potential of the substrate 9 is reduced as a whole. Thereby, similarly to the substrate processing apparatus 10 shown in FIG. 1, device damage due to the movement of charges, that is, damage to the substrate 9 is prevented during the SPM process for the substrate 9 after the charge removal process. Can do. Moreover, in the substrate processing apparatus 10b, the substrate processing apparatus 10b can be reduced in size by providing the neutralization liquid wetted part 7a in the single wafer processing apparatus 1.

  In the substrate processing apparatus 10b, the charge removal process on the substrate 9 is performed in a state where the substrate rotation mechanism 42 is substantially stopped. Thereby, the charge removal of the board | substrate 9 can be performed efficiently. The state in which the substrate rotation mechanism 42 is substantially stopped is not only the state in which the rotation of the substrate 9 by the substrate rotation mechanism 42 is completely stopped as described above, but also the substrate 9 is rotated at a low speed by the substrate rotation mechanism 42. The number of rotations (for example, 10 to 200 rpm) includes a state in which the rotation does not substantially affect the layer of the charge removal liquid on the substrate 9.

  The substrate processing apparatuses 10, 10a, and 10b described above can be variously changed.

  In the substrate processing apparatus 10, for example, the temperature or specific resistance of the static elimination liquid stored in the static elimination liquid storage part 71 may be measured by the static elimination liquid measuring part 62. In addition, a mechanism for heating or cooling the static elimination liquid in the static elimination liquid storage part 71 as necessary may be provided as the temperature adjustment part 61.

  In the charge removal process in the substrate processing apparatus 10b, if the layer of the charge removal liquid on the upper surface 91 of the substrate 9 is maintained without breaking, the supply of the charge removal liquid to the upper surface 91 and the paddle process are performed by rotating the substrate 9. It may be performed in a state where Further, the paddle treatment with the charge removal liquid on the upper surface 91 of the substrate 9 may be performed before or in parallel with the supply of the charge removal liquid to the lower surface 92 of the substrate 9.

  If no adverse effect occurs due to the mixing of the charge removal liquid and the processing liquid, the drying process in step S15 may be omitted in the substrate processing apparatus 10. Moreover, in the substrate processing apparatus 10b, the process of step S17 may be performed without removing the charge removal solution from the substrate 9 in step S16.

  In the above-described substrate processing apparatus, a processing liquid other than the SPM liquid may be supplied onto the substrate 9 and other processing may be performed on the substrate 9. For example, the substrate 9 may be etched by supplying buffered hydrofluoric acid (BHF) as a treatment liquid onto the substrate 9 on which the resist film is formed. In the substrate processing apparatus, as described above, since the substrate 9 can be prevented from being damaged due to the rapid movement of the electric charge due to the contact between the charged substrate 9 and the processing liquid, the structure of the substrate processing apparatus includes an SPM liquid, It is particularly suitable for an apparatus such as buffered hydrofluoric acid in which processing with a processing solution having a very low specific resistance is performed.

  In the above-described substrate processing apparatus, a neutralizing solution obtained by dissolving ammonia in pure water or a solution obtained by adding a small amount of diluted hydrochloric acid to pure water may be used, or a liquid containing various other ions may be used. May be. Furthermore, the neutralizing liquid is pure water or a liquid containing ions, as long as the specific resistance is higher than that of the processing liquid used in the single wafer processing apparatus 1 in at least a predetermined temperature range from the freezing point to the boiling point. Is not limited, and various types of liquids may be used as the charge removal liquid.

  In the substrate processing apparatus, the target temperature and target specific resistance of the static elimination liquid are determined based on conditions other than the size of the device (for example, the type of processing performed on the substrate before being carried into the substrate processing apparatus). May be.

  The configurations in the above-described embodiments and modifications may be combined as appropriate as long as they do not contradict each other.

DESCRIPTION OF SYMBOLS 2 Substrate holding | maintenance part 3 Processing liquid supply part 7, 7a Electrostatic removal liquid contact part 8 Control part 9 Substrate 10, 10a, 10b Substrate processing apparatus 61 Temperature adjustment part 62 Electric discharge liquid measurement part 71, 71a Electric discharge liquid storage part 91 Upper surface 92 Lower surface 95 Static elimination liquid 725 Static elimination liquid nozzle 761 Lower surface liquid contact part S11-S21, S31, S41-S44, S121-S126, S321-S326, S611-S623, S631-S634 Step

Claims (31)

A substrate processing apparatus for processing a substrate,
A substrate holder for holding the substrate;
A processing liquid supply unit for supplying a processing liquid onto the first main surface which is one main surface of the substrate;
A neutralization liquid wetted part for contacting the first major surface of the substrate and the second major surface, which is the other major surface, with a neutralization liquid whose specific resistance gradually decreases as the liquid temperature rises;
A temperature adjusting unit for adjusting the temperature of the static elimination liquid;
By controlling the treatment liquid supply unit, the neutralization liquid wetted part, and the temperature adjustment unit, the temperature of the neutralization liquid is set within a range in which the specific resistance of the neutralization liquid is larger than the specific resistance of the treatment liquid. Meanwhile, after the charge on the substrate is reduced by maintaining the liquid contact state by bringing the first main surface and the second main surface of the substrate into contact with the charge removal solution over the entire surface, the treatment liquid A control unit that performs a predetermined process by supplying the first main surface of the substrate,
A substrate processing apparatus comprising: The substrate processing apparatus according to claim 1,
The substrate processing apparatus, wherein the static elimination liquid in contact with the first main surface and the static elimination liquid in contact with the second main surface are continuous on the substrate. The substrate processing apparatus according to claim 2,
The static elimination liquid contact part includes a static elimination liquid storage part for storing the static elimination liquid,
The substrate processing apparatus according to claim 1, wherein the first main surface and the second main surface are in contact with the charge removal solution by immersing the substrate in the charge removal solution stored in the charge removal solution storage section. The substrate processing apparatus according to claim 3, wherein
A substrate characterized in that a plurality of substrates including the substrate and arranged so that the normal direction of each main surface faces a horizontal direction is immersed in the charge removal solution stored in the charge removal liquid storage unit Processing equipment. The substrate processing apparatus according to claim 1,
The static elimination liquid wetted part is
The neutralization liquid is supplied onto the first principal surface of the substrate held by the substrate holding portion with the first principal surface facing upward, and the entire first principal surface is padded with the neutralization liquid. A first static elimination liquid wetted part
A second discharge liquid wetted part facing the second main surface of the substrate and discharging the discharge liquid toward the second main surface to bring the entire second main surface into contact with the discharge liquid;
A substrate processing apparatus comprising: A substrate processing apparatus according to any one of claims 1 to 5,
A static elimination liquid measuring unit for measuring the temperature of the static elimination liquid;
The substrate processing apparatus, wherein the control unit controls the temperature adjusting unit so that a difference between the temperature of the neutralizing liquid and a predetermined target temperature is reduced based on a measurement result of the neutralizing liquid measuring unit. . The substrate processing apparatus according to claim 6,
The substrate processing apparatus according to claim 1, wherein when the difference between the temperature of the static elimination liquid and the target temperature is equal to or less than a threshold temperature difference, temperature adjustment of the static elimination liquid by the temperature adjustment unit is stopped. The substrate processing apparatus according to claim 6 or 7, wherein
A substrate processing apparatus, wherein a lower target temperature is set as a size of a device formed in advance on the substrate is smaller. A substrate processing apparatus according to any one of claims 1 to 5,
A static elimination liquid measuring unit for measuring the specific resistance of the static elimination liquid;
The substrate, wherein the control unit controls the temperature adjusting unit so that a difference between a specific resistance of the neutralizing liquid and a predetermined target specific resistance becomes small based on a measurement result of the neutralizing liquid measuring unit. Processing equipment. The substrate processing apparatus according to claim 9, comprising:
The substrate processing apparatus, wherein when the difference between the specific resistance of the static elimination liquid and the target specific resistance is equal to or less than a threshold specific resistance difference, temperature adjustment of the static elimination liquid by the temperature adjustment unit is stopped. The substrate processing apparatus according to claim 9 or 10, wherein
The substrate processing apparatus, wherein a target specific resistance having a higher specific resistance is set as a size of a device formed in advance on the substrate is smaller. A substrate processing apparatus according to claim 1,
A liquid removal unit for removing liquid on the first main surface of the substrate;
The control unit controls the liquid removing unit to remove the static eliminating liquid from the first main surface between the contact of the substrate with the static eliminating liquid and the predetermined treatment with the processing liquid. A substrate processing apparatus. The substrate processing apparatus according to any one of claims 1 to 12,
The substrate processing apparatus, wherein the charge eliminating liquid is pure water. The substrate processing apparatus according to claim 1,
The substrate processing apparatus, wherein the processing liquid contains sulfuric acid. A substrate processing method for processing a substrate, comprising:
a) a step of setting the temperature of the static elimination liquid at which the specific resistance gradually decreases as the liquid temperature rises within a range in which the specific resistance of the static elimination liquid is larger than the specific resistance of the treatment liquid;
b) After the step a), reducing the charge on the substrate by bringing the main surfaces on both sides of the substrate into contact with the charge-removing solution over the entire surface and maintaining the liquid contact state;
c) after the step b), supplying the processing liquid onto one main surface of the substrate to perform a predetermined process;
A substrate processing method comprising: The substrate processing method according to claim 15, comprising:
The substrate processing method, wherein the static elimination liquid that contacts the one main surface of the substrate and the static elimination liquid that contacts the other main surface of the substrate are continuous on the substrate. The substrate processing method according to claim 16, comprising:
In the step b), the one main surface and the other main surface are in contact with the charge removal solution by immersing the substrate in the charge removal solution stored in the charge removal solution storage section. Substrate processing method. The substrate processing method according to claim 17,
In the step b), a plurality of substrates including the substrate and arranged so that the normal direction of each main surface thereof is in the horizontal direction are immersed in the charge removal solution stored in the charge removal solution storage section. And a substrate processing method. The substrate processing method according to claim 15, comprising:
Step b)
b1) supplying the charge-removing solution onto the one principal surface of the substrate held with the one principal surface facing upward, and padding the entire one principal surface with the charge-removing solution; ,
b2) discharging the static elimination liquid toward the other main surface of the substrate to bring the entire other main surface into contact with the static elimination liquid;
A substrate processing method comprising: The substrate processing method according to any one of claims 15 to 19,
Step a)
a1) a step of measuring the temperature of the static elimination liquid;
a2) adjusting the temperature of the static elimination liquid so that the difference between the temperature of the static elimination liquid and a predetermined target temperature is reduced based on the measurement result in the a1) step;
a3) repeating the a1) step and the a2) step;
A substrate processing method comprising: The substrate processing method according to any one of claims 15 to 19,
Step a)
a1) a step of measuring the temperature of the static elimination liquid;
a2) Based on the measurement result in the step a1), when the difference between the temperature of the static elimination liquid and a predetermined target temperature is equal to or less than a threshold temperature difference, the temperature of the static elimination liquid is not adjusted without adjusting the temperature of the static elimination liquid. When the difference from the target temperature is larger than the threshold temperature difference, adjusting the temperature of the static elimination liquid so as to reduce the difference between the temperature of the static elimination liquid and the target temperature;
A substrate processing method comprising: The substrate processing method according to claim 20 or 21,
A substrate processing method, wherein a lower target temperature is set as a size of a device formed in advance on the substrate is smaller. The substrate processing method according to any one of claims 20 to 22,
Prior to step a)
d1) obtaining a specific resistance of the treatment liquid;
d2) obtaining a relationship between the temperature of the static elimination liquid and the specific resistance;
d3) obtaining the temperature of the static elimination liquid at which the specific resistance of the static elimination liquid becomes equal to the specific resistance of the treatment liquid based on the relationship obtained in the step d2);
d4) setting a temporary target temperature lower than the temperature acquired in the step d3);
d5) preparing a static elimination liquid at the temporary target temperature;
d6) reducing the charge on the test substrate by bringing the main surfaces on both sides of the test substrate into contact with the static elimination liquid at the temporary target temperature over the entire surface to maintain the liquid contact state;
d7) supplying the processing liquid onto one main surface of the test substrate to perform the predetermined processing;
d8) a step of evaluating the state of the one main surface of the test substrate after completion of the step d7);
d9) If the state of the one main surface is good, the temporary target temperature is set as the target temperature. If the state of the one main surface is not good, the state of the one main surface is good. Until the temporary target temperature is lowered, the steps d5) to d8) are repeated, and the temporary target temperature when the state becomes good is determined as the target temperature;
A substrate processing method, further comprising: The substrate processing method according to any one of claims 20 to 22,
Prior to step a)
d1) obtaining a specific resistance of the treatment liquid;
d2) setting a temporary target specific resistance higher than the specific resistance of the treatment liquid;
d3) obtaining a relationship between the temperature of the static elimination liquid and the specific resistance;
d4) Based on the relationship obtained in the step d3), the temperature of the static elimination liquid at which the specific resistance of the static elimination liquid becomes equal to the temporary target specific resistance set in the step d2). As a process of obtaining as
d5) preparing a static elimination liquid at the temporary target temperature;
d6) reducing the charge on the test substrate by bringing the main surfaces on both sides of the test substrate into contact with the static elimination liquid at the temporary target temperature over the entire surface to maintain the liquid contact state;
d7) supplying the processing liquid onto one main surface of the test substrate to perform the predetermined processing;
d8) a step of evaluating the state of the one main surface of the test substrate after completion of the step d7);
d9) If the state of the one main surface is good, the temporary target temperature is set as the target temperature. If the state of the one main surface is not good, the state of the one main surface is good. Until the temporary target temperature is lowered, the steps d5) to d8) are repeated, and the temporary target temperature when the state becomes good is determined as the target temperature;
A substrate processing method, further comprising: 25. The substrate processing method according to claim 23 or 24, wherein:
If the state of the one main surface is not good between the step d8) and the step d9), the processing time of the step d6) is changed and the steps d6) to d8) are performed. A substrate processing method, further comprising: The substrate processing method according to any one of claims 15 to 19,
Step a)
a1) a step of measuring the specific resistance of the static elimination liquid;
a2) a step of adjusting the temperature of the static elimination liquid so that a difference between a specific resistance of the static elimination liquid and a predetermined target specific resistance is reduced based on a measurement result in the a1) step;
a3) repeating the a1) step and the a2) step;
A substrate processing method comprising: The substrate processing method according to any one of claims 15 to 19,
Step a)
a1) a step of measuring the specific resistance of the static elimination liquid;
a2) Based on the measurement result in the step a1), when the difference between the specific resistance of the static elimination liquid and a predetermined target specific resistance is less than or equal to a threshold specific resistance difference, the temperature of the static elimination liquid is not adjusted, and the static elimination liquid When the difference between the specific resistance and the target specific resistance is larger than the threshold specific resistance difference, the temperature of the static elimination liquid is adjusted so that the difference between the specific resistance of the static elimination liquid and the target specific resistance is small. Process,
A substrate processing method comprising: 28. A substrate processing method according to claim 26 or 27, wherein:
A substrate processing method, wherein a target specific resistance having a larger specific resistance is set as a size of a device formed in advance on the substrate is smaller. A substrate processing method according to any one of claims 15 to 28, comprising:
e) A substrate processing method further comprising a step of removing the charge removal solution from the first main surface of the substrate between the step b) and the step c). A substrate processing method according to any one of claims 15 to 29, comprising:
A substrate processing method, wherein the charge eliminating liquid is pure water. A substrate processing method according to any one of claims 15 to 30, comprising:
A substrate processing method, wherein the processing liquid contains sulfuric acid.

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