JP6118309B2 - Substrate processing method - Google Patents

Description

The present invention relates to a substrate processing method for processing a substrate. Examples of substrates to be processed include semiconductor wafers, liquid crystal display substrates, plasma display substrates, FED (Field Emission Display) substrates, optical disk substrates, magnetic disk substrates, magneto-optical disk substrates, and photomasks. Substrate, ceramic substrate, solar cell substrate and the like.

  In the manufacturing process of a semiconductor device or a liquid crystal display device, a substrate such as a semiconductor wafer or a glass substrate for a liquid crystal display device is processed, for example, one by one. Specifically, the surface of the substrate is treated with the chemical solution by supplying the chemical solution to the substrate. Thereafter, pure water is supplied to the substrate, so that the chemical solution adhering to the substrate is washed away. After the chemical solution is washed away, IPA (isopropyl alcohol) having a boiling point lower than that of water is supplied to the substrate, and the pure water adhering to the substrate is replaced with IPA. Thereafter, when the substrate is rotated at a high speed, IPA adhering to the substrate is removed from the substrate, and the substrate is dried.

  However, in such a substrate processing method, a pattern formed on the surface of the substrate may collapse when the substrate is dried. Therefore, Patent Document 1 discloses a method of drying the surface of the substrate after making it hydrophobic in order to prevent the pattern from collapsing. Specifically, the surface of the substrate is hydrophobized by supplying a hydrophobizing agent to the substrate. Thereafter, IPA is supplied to the substrate, and the hydrophobizing agent adhering to the substrate is replaced with IPA. After the hydrophobizing agent is replaced with IPA, pure water is supplied to the substrate, whereby IPA adhering to the substrate is replaced with pure water. Thereafter, the substrate is rotated at a high speed to dry the substrate.

Japanese Patent No. 4403202

  If the surface of the substrate is sufficiently hydrophobized, the collapse of the pattern can be suppressed. However, when the surface of the substrate is not sufficiently hydrophobized, the collapse of the pattern cannot be suppressed. In other words, if the surface of the substrate is only partially hydrophobized, or if the contact angle of the treatment liquid with respect to the substrate is not sufficiently large, the pattern collapses even if the substrate is hydrophobized and then dried. It cannot be suppressed.

  Further, when the surface tension of the processing liquid adhering to the substrate is large, a force applied to the pattern is large when the substrate is dried. In the substrate processing method described in Patent Document 1, a substrate to which pure water is attached is dried. However, since the surface tension of pure water is large, the collapse of the pattern may not be sufficiently suppressed even if the substrate is hydrophobized. Furthermore, when pure water is supplied to a hydrophobized substrate, the hydrophobicity of the substrate may decrease.

Therefore, an object of the present invention is to provide a substrate processing method capable of suppressing or preventing pattern collapse.

In the first aspect of the invention, the pattern of the laminated film including the first and second films laminated so that one is positioned on the other protrudes from the surface, and the first and second films are mutually connected. A substrate processing method for processing a substrate of different types, wherein each of the first and second films contains silicon or a metal , wherein a first solvent capable of dissolving a first hydrophobizing agent is used as the substrate. After the first solvent rinsing step and the first solvent rinsing step are performed, the first hydrophobizing agent is supplied to the substrate while the first solvent is attached to the substrate. After the first hydrophobizing step for hydrophobizing the surface of the first film and the first hydrophobizing step, the second hydrophobizing agent and the first hydrophobizing agent are different from the first hydrophobizing agent. The second hydrophobizing agent is a second solvent capable of dissolving A second solvent rinse step of supplying the substrate in a state attached to the serial board, attached after the second solvent rinsing step is performed, the second hydrophobizing agent, said second solvent to said substrate A second hydrophobizing step for hydrophobizing the surface of the second film by supplying the substrate to the substrate in a state where the second hydrophobizing step is performed, and a drying step for drying the substrate after the second hydrophobizing step is performed. And at least one of the first hydrophobizing step and the second hydrophobizing step includes a step of diluting a hydrophobizing agent with a diluting solvent capable of dissolving the first solvent and the second solvent, and diluting with the diluting solvent. Supplying the prepared hydrophobizing agent to the substrate as the first hydrophobizing agent or the second hydrophobizing agent.

  According to a second aspect of the present invention, in the pattern, the first and second films are laminated in the order of the first film and the second film from the side close to the surface of the substrate. 1. The substrate processing method according to 1.

  The invention according to claim 3 is the substrate processing method according to claim 1, wherein the first film is a film containing a metal, and the second film is a film containing silicon.

  The invention according to claim 4 is the film according to claim 1 or 2, wherein the first film is a film containing silicon, and the second film is a film containing silicon different from the first film. This is a substrate processing method.

According to a fifth aspect of the present invention, the first hydrophobizing step includes a first vapor supplying step of supplying vapor of the first hydrophobizing agent to the substrate, and the second hydrophobizing step includes the second hydrophobizing step. the vapor of the hydrophobizing agent comprises a second steam supply step of supplying to said substrate, said drying step comprises evaporating step of evaporating the second hydrophobizing agent adhering to the substrate, according to claim 1-4 The substrate processing method according to any one of the above.

Invention of Claim 6 is a substrate processing method as described in any one of Claims 1-5 whose said dilution solvent is a solvent whose surface tension is smaller than water and whose boiling point is lower than water. There is .

  The control means supplies the first hydrophobizing agent to the substrate to hydrophobize the surface of the first film, and after the first hydrophobizing step, the second hydrophobizing step is performed. A second hydrophobizing step of supplying a hydrophobizing agent to the substrate to hydrophobize the surface of the second film, and a drying step of drying the substrate after the second hydrophobizing step is performed. To do.

1 is a schematic diagram showing a schematic configuration of a substrate processing apparatus according to a first embodiment of the present invention. 1 is a schematic diagram showing a schematic configuration of a substrate processing apparatus according to a first embodiment of the present invention. It is a block diagram for demonstrating the electrical constitution of the substrate processing apparatus which concerns on 1st Embodiment of this invention. It is a schematic diagram which shows schematic structure of the 1st hydrophobizing agent supply unit which concerns on 1st Embodiment of this invention. It is process drawing for demonstrating the 1st process example when processing a board | substrate with the substrate processing apparatus which concerns on 1st Embodiment of this invention. It is process drawing for demonstrating the 2nd process example when processing a board | substrate with the substrate processing apparatus which concerns on 1st Embodiment of this invention. It is sectional drawing which shows an example of the board | substrate processed by the substrate processing apparatus which concerns on 1st Embodiment of this invention. It is a table | surface for demonstrating the hydrophobizing agent used when a 1st film | membrane, a 2nd film | membrane, and a 3rd film | membrane are a film | membrane containing silicon, a film | membrane containing silicon, and a metal film, respectively. It is a table | surface for demonstrating the hydrophobizing agent used when a 1st film | membrane, a 2nd film | membrane, and a 3rd film | membrane are a SiN film | membrane, a BSG film | membrane, and a polysilicon film, respectively. It is a table | surface for demonstrating the hydrophobizing agent used when a 1st film | membrane, a 2nd film | membrane, and a 3rd film | membrane are a SiN film | membrane, a metal film, and arbitrary films, respectively. For SiO ₂ and TiN test pieces was immersed in silicon hydrophobizing agent is a graph showing the contact angle of pure water. It is a graph showing the contact angle of pure water with respect to SiO ₂ and TiN specimens immersed in the metal-based hydrophobizing agent. It is a graph showing the contact angle of pure water with respect to silicon hydrophobizing agent and SiO 2 which are sequentially immersed in the metal-based hydrophobizing agent, _TiN and W of the test specimen. It is a graph which shows the contact angle before and behind the rinse process of the compound containing the metal immersed in the metal hydrophobizing agent. It is a schematic diagram which shows the change of the surface state of SiN when the silicon hydrophobizing agent I and the silicon hydrophobizing agent II are sequentially supplied to SiN. It is sectional drawing of the board | substrate for demonstrating the force added to a pattern. It is a schematic diagram which shows schematic structure of the substrate processing apparatus which concerns on 2nd Embodiment of this invention. It is a schematic diagram which shows schematic structure of the 1st hydrophobization agent supply unit which concerns on 2nd Embodiment of this invention. It is process drawing for demonstrating the 3rd process example when processing a board | substrate with the substrate processing apparatus which concerns on 2nd Embodiment of this invention. It is process drawing for demonstrating the 4th process example when processing a board | substrate with the substrate processing apparatus which concerns on 2nd Embodiment of this invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
1 and 2 are schematic views each showing a schematic configuration of a substrate processing apparatus 1 according to the first embodiment of the present invention. FIG. 3 is a block diagram for explaining the electrical configuration of the substrate processing apparatus 1 according to the first embodiment of the present invention.
The substrate processing apparatus 1 is a single-wafer type substrate processing apparatus that processes substrates W such as semiconductor wafers one by one with a processing solution such as a chemical solution or a rinse solution. As shown in FIG. 1 and FIG. 2, the substrate processing apparatus 1 includes a spin chuck 2 (substrate holding means, substrate drying means) that horizontally holds and rotates a substrate W, and a shield disposed above the spin chuck 2. A plate 3 and a processing liquid supply mechanism 4 for supplying a processing liquid to the substrate W held on the spin chuck 2 are provided.

  The spin chuck 2 is, for example, a sandwiching type substrate holding mechanism that sandwiches and holds the substrate W. The spin chuck 2 includes, for example, a disc-shaped spin base 5 that is horizontally disposed, a plurality of clamping members 6 that are disposed on the spin base 5, and a spin motor 7 that is coupled to the spin base 5. The spin chuck 2 can sandwich the substrate W from the periphery by bringing each sandwiching member 6 into contact with the peripheral end surface of the substrate W. Further, the spin chuck 2 can rotate the substrate W around a vertical rotation axis passing through the center of the substrate W by inputting the driving force of the spin motor 7 to the spin base 5 while holding the substrate W. . The spin chuck 2 is not limited to the clamping type substrate holding mechanism, but may be another type of substrate holding mechanism such as a vacuum type that sucks and holds the lower surface (back surface) of the substrate W.

  Moreover, the blocking plate 3 is disk shape, for example. The diameter of the blocking plate 3 is, for example, substantially the same as the diameter of the substrate W or slightly larger than the diameter of the substrate W. The shielding plate 3 is disposed so that the lower surface of the shielding plate 3 is horizontal. Further, the blocking plate 3 is arranged so that the central axis of the blocking plate 3 is positioned on the rotation axis of the spin chuck 2. The lower surface of the blocking plate 3 faces the upper surface of the substrate W held by the spin chuck 2. The blocking plate 3 is connected to the lower end of the support shaft 8 in a horizontal posture. The blocking plate 3 and the support shaft 8 are lifted and lowered in the vertical direction by the blocking plate lifting mechanism 9. The shielding plate lifting mechanism 9 includes a processing position (position shown in FIG. 2) in which the lower surface of the shielding plate 3 is close to the upper surface of the substrate W held by the spin chuck 2, and a retracted position (see FIG. 2) provided above the processing position. 1) is moved up and down.

  The processing liquid supply mechanism 4 includes a chemical liquid nozzle 10, a chemical liquid supply pipe 11, and a chemical liquid valve 12. The chemical liquid supply pipe 11 is connected to the chemical liquid nozzle 10. The chemical liquid valve 12 is interposed in the chemical liquid supply pipe 11. When the chemical solution valve 12 is opened, the chemical solution is supplied from the chemical solution supply pipe 11 to the chemical solution nozzle 10. Further, when the chemical liquid valve 12 is closed, the supply of the chemical liquid from the chemical liquid supply pipe 11 to the chemical liquid nozzle 10 is stopped. The chemical nozzle 10 is connected to the nozzle moving mechanism 13. The nozzle moving mechanism 13 is a chemical solution between a processing position (position shown in FIG. 1) provided above the spin chuck 2 and a retreat position (position shown in FIG. 2) provided at a position away from the processing position. The nozzle 10 is moved. The processing position is set so that the chemical solution discharged from the chemical solution nozzle 10 is supplied to the center of the upper surface of the substrate W held by the spin chuck 2 (see FIG. 1).

  The processing liquid supply mechanism 4 includes a central axis nozzle 14 and a processing liquid supply pipe 15. The central axis nozzle 14 is disposed along the central axis of the blocking plate 3. The central shaft nozzle 14 extends vertically within the support shaft 8. The central shaft nozzle 14 moves up and down together with the blocking plate 3 and the support shaft 8. The processing liquid supply pipe 15 is connected to the central axis nozzle 14 above the blocking plate 3. For example, a processing liquid such as a hydrophobizing agent, a solvent, and a rinsing liquid is supplied from the processing liquid supply pipe 15 to the central axis nozzle 14. The processing liquid supplied to the central axis nozzle 14 is discharged downward from the lower end of the central axis nozzle 14. Then, the processing liquid discharged from the central axis nozzle 14 is discharged downward from the central portion of the lower surface of the blocking plate 3 through a through hole (not shown) that vertically penetrates the central portion of the blocking plate 3 ( (See FIG. 2). As a result, the processing liquid is supplied to the center of the upper surface of the substrate W held by the spin chuck 2.

  The treatment liquid supply mechanism 4 includes two hydrophobizing agent supply units 16 and 17, a solvent supply pipe 19 provided with a solvent valve 18 (solvent supply means), and a rinse liquid valve 20 (rinse liquid supply means). And the rinse liquid supply pipe 21 mounted. The treatment liquid supply pipe 15 is connected to each of the hydrophobizing agent supply units 16 and 17, the solvent supply pipe 19, and the rinse liquid supply pipe 21. The first hydrophobizing agent (liquid) is supplied from the first hydrophobizing agent supply unit 16 to the treatment liquid supply pipe 15. The second hydrophobizing agent (liquid) is supplied from the second hydrophobizing agent supply unit 17 to the treatment liquid supply pipe 15. When the solvent valve 18 is opened, the solvent (liquid) is supplied from the solvent supply pipe 19 to the processing liquid supply pipe 15. Similarly, when the rinse liquid valve 20 is opened, the rinse liquid is supplied from the rinse liquid supply pipe 21 to the treatment liquid supply pipe 15.

The rinse liquid is a liquid containing water. The rinse liquid is, for example, any of pure water (deionized water), carbonated water, electrolytic ion water, hydrogen water, ozone water, and hydrochloric acid water having a diluted concentration (for example, about 10 to 100 ppm).
The first hydrophobizing agent and the second hydrophobizing agent are different types of hydrophobizing agents. The first hydrophobizing agent and the second hydrophobizing agent are liquids that do not contain water. The first hydrophobizing agent is, for example, a silicon hydrophobizing agent that hydrophobizes silicon itself and a compound containing silicon, or a metal hydrophobizing agent that hydrophobizes a compound containing metal itself and a metal. The same applies to the second hydrophobizing agent.

The metal hydrophobizing agent includes, for example, at least one of an amine having a hydrophobic group and an organosilicon compound.
The silicon hydrophobizing agent is, for example, a silane coupling agent. The silane coupling agent includes, for example, at least one of HMDS (hexamethyldisilazane), TMS (tetramethylsilane), fluorinated alkylchlorosilane, alkyldisilazane, and non-chlorohydrophobizing agent.

Non-chloro hydrophobizing agents include, for example, dimethylsilyldimethylamine, dimethylsilyldiethylamine, hexamethyldisilazane, tetramethyldisilazane, bis (dimethylamino) dimethylsilane, N, N-dimethylaminotrimethylsilane, N- (trimethylsilyl) ) Containing at least one of dimethylamine and an organosilane compound.
The solvent is a liquid that can dissolve the hydrophobizing agent and water and does not contain water. Examples of the solvent include at least one of alcohol, ketone, PGMEA (propylene glycol monomethyl ether acetate), EGMEA (ethylene glycol monomethyl ether), and a fluorine-based solvent. The solvent has a lower surface tension than water and a lower boiling point than water.

The alcohol includes, for example, at least one of methyl alcohol, ethanol, propyl alcohol, and IPA (isopropyl alcohol).
The ketone includes, for example, at least one of acetone and diethyl ketone.
The fluorine-based solvent includes, for example, at least one of HFE (hydrofluoroether) and HFC (hydrofluorocarbon).

  As shown in FIG. 3, the substrate processing apparatus 1 includes a control device 22. The spin motor 7, the blocking plate elevating mechanism 9, the nozzle moving mechanism 13, and the hydrophobizing agent supply units 16 and 17 are controlled by the control device 22. The opening / closing of each valve provided in the substrate processing apparatus 1 is controlled by the control device 22. As shown in FIG. 1, the control device 22 causes the chemical liquid nozzle 10 to be positioned at the processing position while the substrate W is rotated by the spin chuck 2, and discharges the chemical liquid from the chemical liquid nozzle 10. The chemical solution discharged from the chemical solution nozzle 10 is supplied to the center of the upper surface of the substrate W held by the spin chuck 2. Then, the chemical solution supplied to the center of the upper surface of the substrate W receives the centrifugal force due to the rotation of the substrate W and spreads outward on the substrate W. Thereby, the chemical solution is supplied to the entire upper surface of the substrate W, and the substrate W is processed by the chemical solution.

  On the other hand, as shown in FIG. 2, the control device 22 causes the blocking plate 3 to be positioned at the processing position while the substrate W is rotated by the spin chuck 2 and discharges the processing liquid from the central axis nozzle 14. The processing liquid discharged from the central axis nozzle 14 is supplied to the central portion of the upper surface of the substrate W held by the spin chuck 2. Then, the processing liquid supplied to the center of the upper surface of the substrate W receives the centrifugal force due to the rotation of the substrate W and spreads outward on the substrate W. Thereby, the processing liquid is supplied to the entire upper surface of the substrate W, and the substrate W is processed with the processing liquid. Further, since the processing liquid is supplied to the substrate W in a state where the lower surface of the blocking plate 3 is close to the upper surface of the substrate W, the processing liquid shaken off around the substrate W is prevented from splashing and adhering to the substrate W. Is prevented.

FIG. 4 is a schematic diagram showing a schematic configuration of the first hydrophobizing agent supply unit 16 according to the first embodiment of the present invention. Hereinafter, a schematic configuration of the first hydrophobizing agent supply unit 16 will be described. Since the schematic configuration of the second hydrophobizing agent supply unit 17 is the same as that of the first hydrophobizing agent supply unit 16, the description thereof is omitted.
The first hydrophobizing agent supply unit 16 includes a first tank 23 storing a first hydrophobizing agent (liquid) and a second tank 24 storing a diluting solvent (liquid). Further, the first hydrophobizing agent supply unit 16 includes a first pipe 25 connected to the first tank 23, a second pipe 26 connected to the second tank 24, and a first pipe 25 interposed in the first pipe 25. 1 valve 27 and first flow rate adjustment valve 28, second valve 29 and second flow rate adjustment valve 30 interposed in second piping 26, and collective piping 31 connected to first piping 25 and second piping 26. Including.

  The first hydrophobizing agent stored in the first tank 23 is, for example, sucked by a pump or supplied with gas into the first tank 23 to increase the atmospheric pressure in the first tank 23. 1 pipe 25 is supplied. The same applies to the diluted solvent. The collective pipe 31 is connected to the processing liquid supply pipe 15 (see FIGS. 1 and 2). The opening and closing of the first valve 27 and the second valve 29 is controlled by the control device 22. The opening degree of the first flow rate adjustment valve 28 and the second flow rate adjustment valve 30 is controlled by the control device 22.

  When the control device 22 opens the first valve 27, the first hydrophobizing agent stored in the first tank 23 is supplied to the collecting pipe 31 at a flow rate corresponding to the opening degree of the first flow rate adjustment valve 28. Similarly, when the control device 22 opens the second valve 29, the diluted solvent stored in the second tank 24 is supplied to the collecting pipe 31 at a flow rate corresponding to the opening degree of the second flow rate adjustment valve 30. As a result, the first hydrophobizing agent and the dilution solvent are mixed in the collecting pipe 31. Therefore, the diluted solvent is dissolved in the first hydrophobizing agent, and the first hydrophobizing agent is diluted. Then, the diluted first hydrophobizing agent is supplied from the collecting pipe 31 to the processing liquid supply pipe 15 and discharged from the central axis nozzle 14. The first hydrophobizing agent may be supplied to the central axis nozzle 14 in a diluted state, or may be supplied to the central axis nozzle 14 without being diluted. For example, when the first hydrophobizing agent is an organosilicon compound which is an example of a metal hydrophobizing agent, the first hydrophobizing agent is preferably supplied to the central shaft nozzle 14 without being diluted.

The dilution solvent is a liquid that can dissolve the above-described hydrophobizing agent and solvent and water and does not contain water. The diluent solvent includes, for example, at least one of alcohol (monohydric alcohol), polyhydric alcohol, ketone, PGMEA, EGMEA, and fluorine-based solvent. The diluted solvent has a lower surface tension than water and a lower boiling point than water.
The alcohol includes, for example, at least one of methyl alcohol, ethanol, propyl alcohol, and IPA.

The polyhydric alcohol includes, for example, ethylene glycol.
The ketone includes, for example, at least one of acetone and diethyl ketone.
The fluorine-based solvent includes, for example, at least one of HFE and HFC.
When the first hydrophobizing agent is an amine having a hydrophobic group, which is an example of a metal hydrophobizing agent, a hydrophilic solvent is used as a dilution solvent. That is, for example, monohydric alcohols such as methyl alcohol, ethanol, IPA, and propyl alcohol, polyhydric alcohols such as ethylene glycol, and ketones such as acetone and diethyl ketone are used as dilution solvents.

  FIG. 5 is a process diagram for explaining a first processing example when the substrate W is processed by the substrate processing apparatus 1 according to the first embodiment of the present invention. Hereinafter, a processing example when processing the substrate W on which the pattern P (see FIG. 7) is formed on the surface that is the device forming surface will be described with reference to FIG. 1, FIG. 2, and FIG. In addition, the “upper surface (front surface) of the substrate W” in the following description includes the upper surface (front surface) of the substrate W itself and the surface of the pattern P.

  The unprocessed substrate W is transported by a transport robot (not shown), and placed on the spin chuck 2 with the surface, which is a device formation surface, facing upward, for example. Then, the control device 22 controls the spin chuck 2 to hold the placed substrate W. When the substrate W is transferred onto the spin chuck 2, the control device 22 moves the chemical nozzle 10 and the blocking plate 3 to prevent the transfer robot and the substrate W from colliding with the chemical nozzle 10 and the blocking plate 3, respectively. It is located in the retreat position.

  Next, a chemical process for supplying the chemical liquid to the substrate W is performed (S101). Specifically, the control device 22 controls the nozzle moving mechanism 13 to move the chemical nozzle 10 from the retracted position to the processing position with the blocking plate 3 positioned at the retracted position. Further, the control device 22 controls the spin motor 7 to rotate the substrate W held on the spin chuck 2. Then, the control device 22 discharges the chemical liquid from the chemical liquid nozzle 10 toward the center of the upper surface of the substrate W while rotating the substrate W by the spin chuck 2. Thereby, the chemical solution is supplied to the entire upper surface of the substrate W, and the substrate W is processed with the chemical solution (chemical solution processing). And if a chemical | medical solution process is performed over predetermined time, the control apparatus 22 will close the chemical | medical solution valve | bulb 12, and will stop the discharge of a chemical | medical solution. Thereafter, the control device 22 controls the nozzle moving mechanism 13 to move the chemical nozzle 10 to the retracted position.

  Next, the water rinse process (water rinse process) which supplies the pure water which is an example of the rinse liquid to the board | substrate W is performed (S102). Specifically, the control device 22 controls the blocking plate lifting mechanism 9 to move the blocking plate 3 from the retracted position to the processing position while the chemical nozzle 10 is positioned at the retracted position. Then, the control device 22 opens the rinse liquid valve 20 and discharges pure water from the central axis nozzle 14 toward the center of the upper surface of the substrate W while rotating the substrate W by the spin chuck 2. Thereby, pure water is supplied to the entire upper surface of the substrate W, and the chemical solution adhering to the substrate W is washed away with pure water (water rinsing process). When the water rinsing process is performed for a predetermined time, the control device 22 closes the rinsing liquid valve 20 and stops the discharge of pure water.

  Next, the 1st solvent rinse process (1st solvent rinse process) which supplies a solvent to the board | substrate W is performed (S103). Specifically, the control device 22 opens the solvent valve 18 to position the blocking plate 3 at the processing position, and further rotates the substrate W by the spin chuck 2 while rotating the substrate W from the center axis nozzle 14 to the center of the upper surface of the substrate W. The solvent is discharged toward the part. Thereby, the solvent discharged from the central axis nozzle 14 is supplied to the entire upper surface of the substrate W as the first solvent. As described above, since the solvent is a liquid capable of dissolving water, the pure water adhering to the substrate W is dissolved in the solvent supplied to the substrate W. Therefore, when the solvent is supplied to the entire upper surface of the substrate W, the pure water adhering to the substrate W is washed away by the solvent and replaced with the solvent (first solvent rinsing process). When the first solvent rinsing process is performed for a predetermined time, the control device 22 closes the solvent valve 18 and stops the discharge of the solvent.

  Next, a first hydrophobizing process for supplying the first hydrophobizing agent (liquid) to the substrate W is performed (S104). Specifically, the control device 22 controls the first hydrophobizing agent supply unit 16 to position the blocking plate 3 at the processing position and further rotate the substrate W by the spin chuck 2 while rotating the central axis nozzle. The first hydrophobizing agent is discharged from 14 toward the center of the upper surface of the substrate W. Thereby, the first hydrophobizing agent is supplied to the entire upper surface of the substrate W. As described above, since the solvent is a liquid capable of dissolving the hydrophobizing agent, the solvent adhering to the substrate W is supplied by supplying the first hydrophobizing agent to the entire upper surface of the substrate W. Replaced by the first hydrophobizing agent. Thereby, the first hydrophobizing agent enters the pattern P, and the upper surface of the substrate W is hydrophobized (first hydrophobizing treatment). When the first hydrophobizing process is performed for a predetermined time, the control device 22 controls the first hydrophobizing agent supply unit 16 to stop the discharge of the first hydrophobizing agent.

  Next, a pre-drying rinsing process (pre-drying rinsing step) for supplying the solvent to the substrate W is performed (S105). Specifically, the control device 22 opens the solvent valve 18 to position the blocking plate 3 at the processing position, and further rotates the substrate W by the spin chuck 2 while rotating the substrate W from the center axis nozzle 14 to the center of the upper surface of the substrate W. The solvent is discharged toward the part. Thereby, the solvent discharged from the central axis nozzle 14 is supplied to the entire upper surface of the substrate W. For this reason, the first hydrophobizing agent adhering to the substrate W is replaced with a solvent (rinse treatment before drying). When the pre-drying rinsing process is performed for a predetermined time, the control device 22 closes the solvent valve 18 and stops the discharge of the solvent.

  Next, a drying process (drying process) for drying the substrate W is performed (S106). Specifically, the control device 22 controls the spin motor 7 to rotate the substrate W at a high rotation speed (for example, several thousand rpm) with the blocking plate 3 positioned at the processing position. Thereby, a large centrifugal force acts on the solvent adhering to the substrate W, and the solvent is shaken off around the substrate W. In this way, the solvent is removed from the substrate W, and the substrate W is dried (drying process). After the drying process is performed for a predetermined time, the control device 22 controls the spin motor 7 to stop the rotation of the substrate W by the spin chuck 2. Further, the control device 22 controls the shield plate lifting mechanism 9 to move the shield plate 3 from the processing position to the retracted position. Thereafter, the processed substrate W is unloaded from the spin chuck 2 by the transfer robot.

  FIG. 6 is a process diagram for explaining a second processing example when the substrate W is processed by the substrate processing apparatus 1 according to the first embodiment of the present invention. Hereinafter, a processing example when processing the substrate W on which the pattern P is formed on the surface which is the device forming surface will be described with reference to FIGS. 1, 2, and 6. In the second processing example, two types of hydrophobizing agents are supplied to the substrate W. In the second processing example, the steps up to the first hydrophobization processing (S104) are the same as those in the first processing example, and therefore, the same reference numerals as those in the first processing example are attached and the description thereof is omitted. Therefore, below, the process after the 1st hydrophobization process is performed is demonstrated.

  After the first hydrophobizing process (S104), a second solvent rinsing process (second solvent rinsing process) for supplying a solvent to the substrate W is performed (S107). Specifically, the control device 22 opens the solvent valve 18 to position the blocking plate 3 at the processing position, and further rotates the substrate W by the spin chuck 2 while rotating the substrate W from the center axis nozzle 14 to the center of the upper surface of the substrate W. The solvent is discharged toward the part. Thereby, the solvent discharged from the central axis nozzle 14 is supplied to the entire upper surface of the substrate W as the second solvent. As described above, since the solvent is a liquid that can dissolve the hydrophobizing agent, when the solvent is supplied to the entire upper surface of the substrate W, the first hydrophobizing agent attached to the substrate W is: The solvent is replaced (second solvent rinsing process). When the second solvent rinsing process is performed for a predetermined time, the control device 22 closes the solvent valve 18 and stops the discharge of the solvent.

  Next, a second hydrophobizing process for supplying the second hydrophobizing agent (liquid) to the substrate W is performed (S108). Specifically, the control device 22 controls the second hydrophobizing agent supply unit 17 to position the blocking plate 3 at the processing position, and further rotate the substrate W by the spin chuck 2 while rotating the central axis nozzle. The second hydrophobizing agent is discharged from 14 toward the center of the upper surface of the substrate W. Thereby, the second hydrophobizing agent is supplied to the entire upper surface of the substrate W. As described above, since the solvent is a liquid that can dissolve the hydrophobizing agent, when the second hydrophobizing agent is supplied to the entire upper surface of the substrate W, the solvent adhering to the substrate W is It is replaced with a second hydrophobizing agent. Thereby, the second hydrophobizing agent enters the pattern P, and the upper surface of the substrate W is hydrophobized (second hydrophobizing treatment). When the second hydrophobizing process is performed for a predetermined time, the control device 22 controls the second hydrophobizing agent supply unit 17 to stop the discharge of the second hydrophobizing agent.

  Next, a pre-drying rinsing process (pre-drying rinsing step) for supplying the solvent to the substrate W is performed (S109). Specifically, the control device 22 opens the solvent valve 18 to position the blocking plate 3 at the processing position, and further rotates the substrate W by the spin chuck 2 while rotating the substrate W from the center axis nozzle 14 to the center of the upper surface of the substrate W. The solvent is discharged toward the part. Thereby, the solvent discharged from the central axis nozzle 14 is supplied to the entire upper surface of the substrate W. Therefore, the second hydrophobizing agent adhering to the substrate W is replaced with a solvent (rinse treatment before drying). When the pre-drying rinsing process is performed for a predetermined time, the control device 22 closes the solvent valve 18 and stops the discharge of the solvent.

  Next, a drying process (drying process) for drying the substrate W is performed (S110). Specifically, the control device 22 controls the spin motor 7 to rotate the substrate W at a high rotation speed (for example, several thousand rpm) with the blocking plate 3 positioned at the processing position. Thereby, a large centrifugal force acts on the solvent adhering to the substrate W, and the solvent is shaken off around the substrate W. In this way, the solvent is removed from the substrate W, and the substrate W is dried (drying process). After the drying process is performed for a predetermined time, the control device 22 controls the spin motor 7 to stop the rotation of the substrate W by the spin chuck 2. Further, the control device 22 controls the shield plate lifting mechanism 9 to move the shield plate 3 from the processing position to the retracted position. Thereafter, the processed substrate W is unloaded from the spin chuck 2 by the transfer robot.

FIG. 7 is a cross-sectional view showing an example of a substrate W processed by the substrate processing apparatus 1 according to the first embodiment of the present invention.
The substrate W processed by the substrate processing apparatus 1 is, for example, the substrate W on which the pattern P of the laminated film 32 is formed. The stacked film 32 includes, for example, a first film 32a, a second film 32b, and a third film 32c. The films 32a, 32b, and 32c are stacked in the order of the third film 32c, the second film 32b, and the first film 32a from the side close to the surface of the substrate W itself. That is, the first film 32a corresponds to an upper layer film with respect to the second film 32b and the third film 32c, and the second film 32b and third film 32c correspond to a lower layer film with respect to the first film 32a. The second film 32b corresponds to an upper layer film with respect to the third film 32c, and the third film 32c corresponds to a lower layer film with respect to the second film 32b. The first film 32a is, for example, any one of a film containing silicon, a nitride film, and a metal film. The same applies to the second film 32b and the third film 32c.

The film containing silicon is, for example, a SiO film formed by a CVD method using a polysilicon film, a SiO ₂ film, a SiN film, a BSG film (a boron containing SiO ₂ film), and a TEOS film (TEOS (tetraethoxysilane)). ₂ films). The SiO ₂ film, BSG film, and TEOS film are also oxide films.
The nitride film is, for example, a SiN film. The SiN film is also a film containing silicon.

The metal film is a film containing at least one of Ti, W, Cu, and Al, for example. The metal film is, for example, either a TiN film or a W film.
Specific examples of the combination of the first film 32a, the second film 32b, and the third film 32c are “a film containing silicon (first film 32a), a film containing silicon (second film 32b), and a metal film (third Film 32c) "," metal film (first film 32a), film containing silicon (second film 32b), film containing silicon (third film 32c) "," SiN film (first film 32a), BSG “Film (second film 32b), polysilicon film (third film 32c)”, “BSG film (first film 32a), TEOS film (second film 32b), polysilicon film (third film 32c)”, “ SiN film (first film 32a), metal film (second film 32b), and arbitrary film (third film 32c) ”. The first film 32a, the second film 32b, and the third film 32c are not limited to these combinations, and may be other combinations.

The film containing silicon is hydrophobized by a silicon hydrophobizing agent. Similarly, the oxide film and the nitride film are hydrophobized by the silicon hydrophobizing agent. The metal film is hydrophobized by a metal hydrophobizing agent.
Hereinafter, specific combinations of the first film 32a, the second film 32b, and the third film 32c, and specific examples of the first hydrophobizing agent and the second hydrophobizing agent used in each combination will be described.

FIG. 8 is a table for explaining a hydrophobizing agent used when the first film 32a, the second film 32b, and the third film 32c are a film containing silicon, a film containing silicon, and a metal film, respectively. It is.
When the first film 32a, the second film 32b, and the third film 32c are a film containing silicon, a film containing silicon, and a metal film, respectively, in the first processing example, for example, a silicon-based hydrophobizing agent or metal A hydrophobizing agent is used as the first hydrophobizing agent. Therefore, the silicon-containing film or metal film is hydrophobized. Although not shown, even when the first film 32a, the second film 32b, and the third film 32c are a metal film, a film containing silicon, and a film containing silicon, respectively, in the first processing example, for example, A silicon hydrophobizing agent or a metal hydrophobizing agent is used as the first hydrophobizing agent.

  On the other hand, in the second processing example, for example, a metal hydrophobizing agent is used as the first hydrophobizing agent, and a silicon hydrophobizing agent is used as the second hydrophobizing agent. That is, after the lower layer film (the third film 32c) is hydrophobized, the upper layer film (the first film 32a and the second film 32b) is hydrophobized, and the substrate W is hydrophobized in the order of the lower layer film and the upper layer film. Therefore, when the first film 32a, the second film 32b, and the third film 32c are a metal film, a film containing silicon, and a film containing silicon, respectively, in the second processing example, for example, a silicon-based hydrophobic film The agent is used as the first hydrophobizing agent, and the metal hydrophobizing agent is used as the second hydrophobizing agent.

  In the case of a substrate W having a silicon-containing film and a metal film, when a hydrophobizing agent containing chlorine (for example, fluorinated alkylchlorosilane) is used as the first hydrophobizing agent or the second hydrophobizing agent, the hydrophobizing agent reacts. As a result, the generated hydrochloric acid reacts with the metal film. Therefore, in the case of the substrate W having the silicon-containing film and the metal film, the hydrophobizing agent that does not contain chlorine (for example, the non-chloro hydrophobizing agent described above) in both the first processing example and the second processing example. ) Is preferably used as the first hydrophobizing agent or the second hydrophobizing agent. Thereby, the reaction between hydrochloric acid and the metal film is prevented.

FIG. 9 is a table for explaining a hydrophobizing agent used when the first film 32a, the second film 32b, and the third film 32c are a SiN film, a BSG film, and a polysilicon film, respectively.
When the first film 32a, the second film 32b, and the third film 32c are a SiN film, a BSG film, and a polysilicon film, respectively, in the first processing example, for example, a silicon hydrophobizing agent is a first hydrophobizing agent. Used as an agent. When the silicon hydrophobizing agent is used as the first hydrophobizing agent, the first film 32a, the second film 32b, and the third film 32c are hydrophobized. On the other hand, when the metal hydrophobizing agent is used as the first hydrophobizing agent, since the first film 32a, the second film 32b, and the third film 32c are films containing silicon, the hydrophobizing performance is Low. Therefore, in the first processing example, it is preferable that a silicon hydrophobizing agent is used as the first hydrophobizing agent.

  On the other hand, in the second processing example, for example, the silicon hydrophobizing agent I is used as the first hydrophobizing agent, and the silicon hydrophobizing agent II is used as the second hydrophobizing agent. When the silicon-based hydrophobizing agent I is supplied to the substrate W as the first hydrophobizing agent, the first film 32a, the second film 32b, and the third film 32c are hydrophobized. Thereafter, when the silicon-based hydrophobizing agent II is supplied to the substrate W as the second hydrophobizing agent, the first film 32a (SiN film) is further hydrophobized. That is, after the SiN film is hydrophobized by the silicon hydrophobizing agent I, the SiN film is further hydrophobized by a different type of silicon hydrophobizing agent II from the silicon hydrophobizing agent I. Thus, after the upper layer film and the lower layer film are hydrophobized, the upper layer film is further hydrophobized. Details of the hydrophobizing treatment with the silicon hydrophobizing agent I and the silicon hydrophobizing agent II will be described later.

FIG. 10 is a table for explaining a hydrophobizing agent used when the first film 32a, the second film 32b, and the third film 32c are a SiN film, a metal film, and an arbitrary film, respectively.
When the first film 32a, the second film 32b, and the third film 32c are a SiN film, a metal film, and an arbitrary film, respectively, in the first treatment example, for example, a silicon hydrophobizing agent (preferably a non-chloroform agent) A hydrophobizing agent) or a metal hydrophobizing agent is used as the first hydrophobizing agent. When the silicon hydrophobizing agent is used as the first hydrophobizing agent, the first film 32a (SiN film) is hydrophobized. On the other hand, when the metal hydrophobizing agent is used as the first hydrophobizing agent, the second film 32b (metal film) is hydrophobized.

  On the other hand, in the second treatment example, for example, a metal hydrophobizing agent is used as the first hydrophobizing agent, and a silicon hydrophobizing agent (preferably a non-chloro hydrophobizing agent) is used as the second hydrophobizing agent. . When the metal hydrophobizing agent is supplied to the substrate W as the first hydrophobizing agent, the second film 32b is hydrophobized. Thereafter, when the silicon-based hydrophobizing agent is supplied to the substrate W as the second hydrophobizing agent, the first film 32a (SiN film) is hydrophobized. Thus, after the lower layer film is hydrophobized, the upper layer film is hydrophobized.

FIG. 11 is a graph showing the contact angle of pure water with respect to a specimen of SiO ₂ and TiN immersed in a silicon hydrophobizing agent. FIG. 12 is a graph showing the contact angle of pure water with respect to the SiO ₂ and TiN test pieces immersed in the metal hydrophobizing agent. FIG. 13 is a graph showing the contact angle of pure water with respect to SiO ₂ , TiN, and W test pieces that are sequentially immersed in a silicon hydrophobizing agent and a metal hydrophobizing agent.

As shown in FIG. 11, the contact angle of pure water with respect to the SiO ₂ test piece immersed in the silicon hydrophobizing agent is 70 degrees or more in any immersion time. Moreover, as shown in FIG. 11, the contact angle of pure water with respect to the TiN test piece immersed in the silicon hydrophobizing agent is 20 degrees or less when the immersion time is 2 minutes or less, and when the immersion time is 3 minutes or more. It is 30 degrees or less.
On the other hand, as shown in FIG. 12, the contact angle of pure water with respect to the test piece of SiO ₂ immersed in the metal hydrophobizing agent is about 40 degrees in any immersion time. Moreover, as shown in FIG. 12, the contact angle of pure water with respect to the test piece of TiN immersed in the metal hydrophobizing agent is about 80 degrees in any immersion time.

From the measured values shown in FIGS. 11 and 12, it can be seen that the silicon hydrophobizing agent can sufficiently hydrophobize the silicon-containing compound (SiO ₂ ), but cannot sufficiently hydrophobize the metal-containing compound (TiN). . Further, it can be seen that the metal hydrophobizing agent can sufficiently hydrophobize the metal-containing compound (TiN), but cannot sufficiently hydrophobize the silicon-containing compound (SiO ₂ ).

On the other hand, as shown in FIG. 13, the contact angles of pure water with respect to the test pieces of SiO ₂ , TiN, and W, which were sequentially immersed in the silicon hydrophobizing agent and the metal hydrophobizing agent, were about 80 degrees and about 70, respectively. Degrees, and about 60 degrees. Therefore, by supplying both the silicon hydrophobizing agent and the metal hydrophobizing agent to the substrate W, the silicon-containing film and the metal film-containing substrate W can be sufficiently hydrophobized.

  FIG. 14 is a graph showing contact angles before and after rinsing treatment of a compound containing a metal immersed in a metal hydrophobizing agent. The contact angle before rinsing in FIG. 14 is a contact angle before a compound containing a metal immersed in an amine having a hydrophobic group, which is an example of a metal hydrophobizing agent, is rinsed. Further, the contact angle after rinsing in FIG. 14 is a contact angle after a compound containing a metal immersed in an amine having a hydrophobic group is rinsed with any one of the solvent A, the solvent B, and pure water. The solvent A and the solvent B are different types of solvents. The solvent A is a solvent used as the first solvent and the second solvent in the first processing example and the second processing example. The same applies to the solvent B.

  As shown in FIG. 14, the contact angle of pure water (contact angle before rinsing) with respect to a compound containing a metal immersed in an amine having a hydrophobic group is about 90 degrees. When this metal-containing compound is washed with solvent A, the contact angle is reduced by about 10 degrees. Further, when the compound containing the metal is washed with the solvent B, the contact angle is reduced by about 15 degrees. Further, when the compound containing the metal is washed with pure water, the contact angle is reduced by about 50 degrees.

  From the measured values shown in FIG. 14, when pure water (liquid containing OH groups) is supplied to a compound containing a metal immersed in an amine having a hydrophobic group, compared to the case where the solvent A and the solvent B are supplied, It can be seen that the contact angle is greatly reduced. Therefore, the pure water is not supplied to the substrate W after the amine having a hydrophobic group is supplied to the substrate W, that is, the pure water does not contact the substrate W, thereby reducing the contact angle of the pure water with respect to the substrate W. Can be suppressed.

FIG. 15 is a schematic diagram showing changes in the surface state of SiN when silicon hydrophobizing agent I and silicon hydrophobizing agent II are sequentially supplied to SiN.
As described above, SiN is hydrophobized by both the silicon hydrophobizing agent I and the silicon hydrophobizing agent II. The hydrophobic group of the silicon hydrophobizing agent II is shorter than the hydrophobic group of the silicon hydrophobizing agent I. That is, the molecular weight of the hydrophobic group of the silicon hydrophobizing agent II is smaller than the molecular weight of the hydrophobic group of the silicon hydrophobizing agent I. The reactivity of the hydrophobizing agent with respect to SiN is higher as the hydrophobic group is shorter. Therefore, the silicon hydrophobizing agent II is more reactive with SiN than the silicon hydrophobizing agent I. On the other hand, if the reactivity with SiN is the same, the longer the hydrophobic group, the greater the contact angle of pure water with SiN. Therefore, the silicon hydrophobizing agent I can hydrophobize SiN more efficiently than the silicon hydrophobizing agent II.

For example, when comparing SiN and SiO ₂ , both are compounds containing silicon, but SiN has fewer functional groups (reactive groups) than SiO ₂ . Therefore, even if silicon-based hydrophobizing agent II is supplied to SiN and SiN functional groups and silicon-based hydrophobizing agent II react efficiently, there are few SiN functional groups and silicon-based hydrophobization. Since the hydrophobic group of the agent II is short, the surface of SiN is not sufficiently hydrophobized. That is, the contact angle does not increase sufficiently.

  On the other hand, although the hydrophobic group of the silicon hydrophobizing agent I is long, the silicon hydrophobizing agent I is less reactive to SiN than the silicon hydrophobizing agent II. Therefore, even if the silicon hydrophobizing agent I is supplied to SiN, a part of the functional group of SiN does not react with the hydrophobic group of the silicon hydrophobizing agent I, so that the hydrophobicity of SiN as a whole does not sufficiently increase. . Therefore, by supplying both silicon hydrophobizing agent I and silicon hydrophobizing agent II to SiN, both silicon hydrophobizing agent I and silicon hydrophobizing agent II are reacted with SiN, and SiN is sufficient. Can be hydrophobized.

  In particular, as shown in FIG. 15, after supplying the silicon hydrophobizing agent I to SiN, the highly reactive silicon hydrophobizing agent II is supplied to SiN, so that the hydrophobic group of the silicon hydrophobizing agent I is removed. While being able to react with the functional group of SiN, the functional group of SiN hydrophobizing agent II can be reacted with the functional group of SiN remaining without reacting with the hydrophobic group of silicon hydrophobizing agent I. Thereby, SiN can fully be hydrophobized. Therefore, it is preferable to supply the silicon hydrophobizing agent II with a short hydrophobic group after supplying the silicon hydrophobizing agent I with a long hydrophobic group to the SiN film.

FIG. 16 is a cross-sectional view of the substrate W for explaining the force applied to the pattern P. FIG.
When the substrate W on which the pattern P is formed is dried, a force that attracts the patterns P is applied in the process of drying the substrate W, and the pattern P may collapse. At this time, the force F applied to the pattern P is expressed by, for example, the following expression (1).
F = (2 × σ × H cos θ) / L (Expression 1)
“Σ” is the surface tension of the treatment liquid, “θ” is the contact angle, “H” is the height of the pattern P, and “L” is the interval between the patterns P.

From this equation (1), it can be seen that the force F applied to the pattern P decreases as the surface tension σ of the treatment liquid decreases. Therefore, by reducing the surface tension σ of the processing liquid, the force F applied to the pattern P can be reduced, and the collapse of the pattern P can be suppressed or prevented.
It can also be seen that the force F applied to the pattern P decreases as the contact angle θ approaches 90 degrees. Therefore, the collapse of the pattern P can be suppressed or prevented by making the surface of the substrate W hydrophobic to bring the contact angle θ close to 90 degrees.

On the other hand, when the surface of the substrate W is not sufficiently hydrophobized, the force F applied to the pattern P is not sufficiently reduced, and the collapse of the pattern P cannot be sufficiently suppressed. Therefore, in order to sufficiently suppress the collapse of the pattern P, it is preferable to sufficiently hydrophobize the entire surface of the substrate W.
In the first processing example and the second processing example described above, the substrate W is hydrophobized by the hydrophobizing agent (first hydrophobizing process and second hydrophobizing process). Thereby, the contact angle of the processing liquid with respect to the substrate W is brought close to 90 degrees. Therefore, the force applied to the pattern P can be reduced, and the collapse of the pattern P can be suppressed or prevented.

  In the second processing example, plural types of hydrophobizing agents are supplied to the substrate W (first hydrophobizing process and second hydrophobizing process). Therefore, when the substrate W on which the pattern P of the laminated film 32 including the silicon film and the metal film is processed, the entire surface of the substrate W can be sufficiently hydrophobized. Furthermore, when processing the substrate W having a nitride film such as a SiN film, the hydrophobicity of the substrate W can be sufficiently increased. Thereby, collapse of the pattern P can be suppressed or prevented.

  In the first processing example and the second processing example, the solvent, the hydrophobizing agent, and the substrate W until the substrate W is hydrophobized and dried (from the end of the first hydrophobizing process to the end of the drying process). A solvent is supplied to the substrate W. The hydrophobizing agent and the solvent are liquids that do not contain water. Therefore, in the first processing example and the second processing example, the pure water is not in contact with the substrate W until the substrate W is dried after being hydrophobized.

  As described with reference to FIG. 14, when pure water is supplied to the substrate W after supplying an amine having a hydrophobic group, which is an example of a metal hydrophobizing agent, to the substrate W including the metal film, Hydrophobicity is greatly reduced. Accordingly, since the state in which pure water is not in contact with the substrate W is maintained until the substrate W is dried after the hydrophobicity of the substrate W, when the amine having a hydrophobic group is supplied to the substrate W, the hydrophobicity of the substrate W is decreased. Is prevented from significantly decreasing. Thereby, collapse of the pattern P can be suppressed or prevented.

In addition, since the state in which pure water does not contact the substrate W is maintained until the substrate W is dried after being hydrophobized, the generation of watermarks can be suppressed or prevented.
In the second treatment example, after the lower layer film is hydrophobized by the first hydrophobizing agent, or after the lower layer film and the upper layer film are hydrophobized by the first hydrophobizing agent, the upper layer film is formed by the second hydrophobizing agent. Is hydrophobized. For example, if the hydrophobizing agent is further supplied to the substrate W after the upper layer film is hydrophobized, the upper layer film is hydrophobized, and thus the hydrophobizing agent may not be sufficiently supplied to the lower layer film. Therefore, after the lower layer film is hydrophobized, or after the lower layer film and the upper layer film are hydrophobized, a second hydrophobizing agent that hydrophobizes the upper layer film is supplied to the substrate W. It can be sufficiently hydrophobized. Thereby, the substrate W can be sufficiently hydrophobized.

  In the first processing example and the second processing example, pure water, which is an example of a rinsing liquid, is supplied to the substrate W (water rinsing process). Thereafter, the solvent is supplied as the first solvent to the substrate W (first solvent rinsing process). Thereby, the pure water adhering to the substrate W is replaced with the solvent. Therefore, the first hydrophobizing agent and the second hydrophobizing agent are supplied to the substrate W in a state where pure water is removed. This prevents the first hydrophobizing agent and the second hydrophobizing agent from coming into contact with pure water. Therefore, when the hydrophobizing agent whose activity decreases by contact with water is used as the first hydrophobizing agent and the second hydrophobizing agent, the activity of the first hydrophobizing agent and the second hydrophobizing agent is increased. Decrease is prevented. Thereby, the substrate W can be sufficiently hydrophobized.

  In the second treatment example, the solvent capable of dissolving the first hydrophobizing agent and the second hydrophobizing agent after the first hydrophobizing treatment and before the second hydrophobizing treatment is performed. Is supplied to the substrate W as the second solvent (second solvent rinsing step). If the first hydrophobizing agent and the second hydrophobizing agent are not easily mixed, even if the second hydrophobizing agent is supplied to the substrate W while the first hydrophobizing agent is attached to the substrate W, the substrate The first hydrophobizing agent attached to W cannot be easily replaced with the second hydrophobizing agent. For this reason, the second hydrophobizing agent does not sufficiently contact the surface of the substrate W.

  On the other hand, the solvent (second solvent) can dissolve the first hydrophobizing agent and the second hydrophobizing agent. Therefore, by supplying the solvent to the substrate W after the first hydrophobization treatment, the first hydrophobizing agent adhering to the substrate W is replaced with the solvent, and the first hydrophobizing agent is removed from the substrate W. Can be removed. Then, by supplying the second hydrophobizing agent to the substrate W after the second solvent rinsing process is performed, the solvent adhering to the substrate W is replaced with the second hydrophobizing agent, and the solvent is removed from the substrate W. Can be removed. Therefore, even when the first hydrophobizing agent and the second hydrophobizing agent are not easily mixed, the first hydrophobizing agent attached to the substrate W can be replaced with the second hydrophobizing agent. . Thereby, the second hydrophobizing agent can be reacted with the substrate W, and the substrate W can be hydrophobized by the second hydrophobizing agent.

  In the first processing example and the second processing example, the solvent is supplied to the substrate W in the pre-drying rinsing process. Then, the solvent adhering to the substrate W is removed, and the substrate W is dried. The solvent supplied to the substrate W in the pre-drying rinsing process has a surface tension smaller than that of water. Therefore, the collapse of the pattern P can be suppressed or prevented as compared with the case where pure water is supplied to the substrate W in the rinsing process before drying. Furthermore, the solvent supplied to the substrate W in the pre-drying rinsing process has a boiling point lower than that of water. Therefore, the substrate W can be dried more quickly than when pure water is supplied to the substrate W in the rinsing process before drying.

  In the first processing example and the second processing example, the first hydrophobizing agent and the second hydrophobizing agent diluted with the diluting solvent are supplied to the substrate W. The dilution solvent can dissolve the solvent used as the first solvent and the second solvent. Therefore, when the first hydrophobizing agent and the second hydrophobizing agent are diluted with the diluting solvent, the affinity between the first hydrophobizing agent and the second hydrophobizing agent and the first solvent and the second solvent is increased. Therefore, the solvent (first solvent and second solvent) adhering to the substrate W can be easily replaced with the first hydrophobizing agent and the second hydrophobizing agent.

  In the first processing example and the second processing example, the hydrophobizing agent (the first hydrophobizing agent and the second hydrophobizing agent) and the diluting solvent are mixed in the collecting pipe 31. That is, the first hydrophobizing agent and the second hydrophobizing agent are diluted with the diluting solvent immediately before being supplied to the substrate W. Therefore, when the hydrophobizing agent whose activity gradually decreases by being diluted with a diluting solvent is used as the first hydrophobizing agent and the second hydrophobizing agent, the first hydrophobizing agent and the second hydrophobizing agent It is prevented that the activity of is significantly reduced. Thereby, the substrate W can be sufficiently hydrophobized.

  FIG. 17 is a schematic diagram showing a schematic configuration of a substrate processing apparatus 201 according to the second embodiment of the present invention. FIG. 18 is a schematic diagram showing a schematic configuration of the first hydrophobizing agent supply unit 216 according to the second embodiment of the present invention. 17 and 18, the same components as those shown in FIGS. 1 to 16 described above are denoted by the same reference numerals as those in FIG. 1 and the description thereof is omitted.

  The main difference between the second embodiment and the first embodiment described above is that, as shown in FIG. 17, the first hydrophobization that supplies the vapor of the first hydrophobizing agent and the vapor of the second hydrophobizing agent, respectively. The substrate processing apparatus 201 includes an agent supply unit 216 (first hydrophobizing agent supply means) and a second hydrophobizing agent supply unit 217 (second hydrophobizing agent supply means). Since the schematic configuration of the first hydrophobizing agent supply unit 216 and the schematic configuration of the second hydrophobizing agent supply unit 217 are the same, the schematic configuration of the first hydrophobizing agent supply unit 216 will be described below.

  As shown in FIG. 18, the first hydrophobizing agent supply unit 216 includes a first tank 23 storing a first hydrophobizing agent (liquid) and a second tank 24 storing a diluting solvent (liquid). Including. Further, the first hydrophobizing agent supply unit 216 includes a heater 233 interposed in the collecting pipe 31 and a carrier gas supply pipe 235 in which a valve 234 is interposed. The carrier gas supply pipe 235 is connected to the collective pipe 31. The temperature of the heater 233 is controlled by the control device 22 (see FIG. 3). The opening / closing of the valve 234 is controlled by the control device 22. When the valve 234 is opened, the carrier gas is supplied to the collecting pipe 31. Examples of the carrier gas include inert gases such as nitrogen gas and argon gas.

  The dilution solvent is the same as that in the first embodiment. In the second embodiment, for example, a solvent containing HFE is used as the dilution solvent. HFE has a lower boiling point than water. Therefore, the boiling point of the diluted first hydrophobizing agent can be lowered by diluting the first hydrophobizing agent with the diluting solvent. Thereby, the diluted 1st hydrophobizing agent can be evaporated easily. HFE is nonflammable. The control device 22 controls the opening degree of the first flow rate adjustment valve 28 and the second flow rate adjustment valve 30 so that the diluted first hydrophobizing agent becomes nonflammable. Therefore, it is not necessary to take measures to prevent the substrate processing apparatus 201 from exploding.

  The control device 22 opens the first valve 27, the second valve 29, and the valve 234, and further heats the collecting pipe 31 by the heater 233. By opening the first valve 27 and the second valve 29, the first hydrophobizing agent (liquid) and the diluting solvent (liquid) are supplied to the collecting pipe 31. The first hydrophobizing agent and diluent solvent supplied to the collecting pipe 31 are mixed in the collecting pipe 31 and then heated by the heater 233. As a result, the liquid mixture of the first hydrophobizing agent and the diluting solvent evaporates, and the diluted liquid of the first hydrophobizing agent changes to vapor. The vapor of the first hydrophobizing agent generated in the collecting pipe 31 is caused to flow toward the central axis nozzle 14 by the carrier gas supplied from the carrier gas supply pipe 235 to the collecting pipe 31. As a result, the vapor of the first hydrophobizing agent is discharged from the central axis nozzle 14.

  As shown in FIG. 17, the control device 22 discharges the vapor of the first hydrophobizing agent and the vapor of the second hydrophobizing agent from the central shaft nozzle 14 with the blocking plate 3 positioned at the processing position. The hydrophobizing agent vapor discharged from the central axis nozzle 14 spreads outward between the blocking plate 3 and the substrate W and is discharged from between the blocking plate 3 and the substrate W. Thereby, the space between the blocking plate 3 and the substrate W is filled with the vapor of the hydrophobizing agent. Further, the hydrophobizing agent vapor discharged from the central axis nozzle 14 flows outward along the upper surface of the substrate W. Thereby, the vapor of the hydrophobizing agent is supplied to the entire upper surface of the substrate W. While the hydrophobizing agent vapor is discharged from the central axis nozzle 14, the substrate W held by the spin chuck 2 may be rotated around a vertical rotation axis passing through the center of the substrate W or in a non-rotating state. It may be held.

  FIG. 19 is a process diagram for explaining a third processing example when the substrate W is processed by the substrate processing apparatus 201 according to the second embodiment of the present invention. Hereinafter, with reference to FIGS. 17 and 19, a processing example when processing the substrate W on which the pattern P is formed on the surface which is the device forming surface will be described. In the third processing example, since the steps up to the first solvent rinsing process (S103) are the same as those in the first processing example, the same reference numerals as those in the first processing example are used, and the description thereof is omitted. Therefore, below, the process after the 1st solvent rinse process is performed is demonstrated.

  After the first solvent rinsing process (S103) is performed, a first hydrophobizing process (first hydrophobizing process, first steam supplying process) for supplying the first hydrophobizing agent (vapor) to the substrate W is performed. (S204). Specifically, the control device 22 controls the first hydrophobizing agent supply unit 216 to direct the central plate nozzle 14 toward the center of the upper surface of the substrate W with the blocking plate 3 positioned at the processing position. Then, the vapor of the first hydrophobizing agent is discharged. The solvent adhering to the substrate W is removed from the substrate W while dissolving in the vapor of the first hydrophobizing agent that flows outward along the upper surface of the substrate W. Further, when the vapor of the first hydrophobizing agent flows outward along the upper surface of the substrate W, the vapor of the first hydrophobizing agent is supplied to the entire upper surface of the substrate W, and the vapor of the first hydrophobizing agent is patterned. Get inside P. Thereby, the upper surface of the substrate W is hydrophobized (first hydrophobizing treatment). When the first hydrophobizing process is performed for a predetermined time, the control device 22 controls the first hydrophobizing agent supply unit 216 to stop the discharge of the first hydrophobizing agent vapor.

  Next, a drying process (drying process, evaporation process) for drying the substrate W is performed (S205). Specifically, the control device 22 dries the substrate W by evaporating the droplets of the first hydrophobizing agent adhering to the upper surface of the substrate W (drying process). The controller 22 may cause the droplets of the first hydrophobizing agent to evaporate by the air flow generated by the rotation of the substrate W by rotating the substrate W by the spin chuck 2, or the first hydrophobicity while the substrate W is stationary. The droplets of the agent may be naturally evaporated. Further, the control device 22 may evaporate the droplets of the first hydrophobizing agent while transporting the substrate W by the transport robot.

  FIG. 20 is a process diagram for explaining a fourth processing example when the substrate W is processed by the substrate processing apparatus 201 according to the second embodiment of the present invention. Hereinafter, with reference to FIGS. 17 and 20, a processing example when processing the substrate W on which the pattern P is formed on the surface which is the device forming surface will be described. In the fourth processing example, vapors of two types of hydrophobizing agents are supplied to the substrate W. In the fourth process example, the steps up to the first hydrophobization process (S204) are the same as those in the third process example, and therefore, the same reference numerals as those in the third process example are given and the description thereof is omitted. Therefore, below, the process after the 1st hydrophobization process is performed is demonstrated.

  After the first hydrophobizing process (S204) is performed, a second solvent rinsing process (second solvent rinsing process) for supplying a solvent to the substrate W is performed (S206). Specifically, the control device 22 opens the solvent valve 18 to position the blocking plate 3 at the processing position, and further rotates the substrate W by the spin chuck 2 while rotating the substrate W from the center axis nozzle 14 to the center of the upper surface of the substrate W. The solvent is discharged toward the part. Thereby, the solvent discharged from the central axis nozzle 14 is supplied to the entire upper surface of the substrate W as the second solvent. As described above, since the solvent is a liquid that can dissolve the hydrophobizing agent, the first hydrophobizing agent adhering to the substrate W is supplied by supplying the solvent to the entire upper surface of the substrate W. The droplet is replaced with a solvent (second solvent rinsing process). When the second solvent rinsing process is performed for a predetermined time, the control device 22 closes the solvent valve 18 and stops the discharge of the solvent.

  After the second solvent rinsing step (S206) is performed, a second hydrophobizing process (second hydrophobizing step, second vapor supplying step) for supplying the second hydrophobizing agent (vapor) to the substrate W is performed. (S207). Specifically, the control device 22 controls the second hydrophobizing agent supply unit 217 to direct the central plate nozzle 14 toward the center of the upper surface of the substrate W with the blocking plate 3 positioned at the processing position. Then, the vapor of the second hydrophobizing agent is discharged. When the vapor of the second hydrophobizing agent flows outward along the upper surface of the substrate W, the vapor of the second hydrophobizing agent is supplied to the entire upper surface of the substrate W, and the vapor of the second hydrophobizing agent is Get inside. Thereby, the upper surface of the substrate W is hydrophobized (second hydrophobizing treatment). When the second hydrophobizing process is performed for a predetermined time, the control device 22 controls the second hydrophobizing agent supply unit 217 to stop the discharge of the vapor of the second hydrophobizing agent.

  Next, a drying process (drying process, evaporation process) for drying the substrate W is performed (S208). Specifically, the control device 22 dries the substrate W by evaporating droplets of the second hydrophobizing agent adhering to the upper surface of the substrate W (drying process). The controller 22 may cause the droplets of the second hydrophobizing agent to evaporate by the air flow generated by the rotation of the substrate W by rotating the substrate W by the spin chuck 2, or the second hydrophobicity while the substrate W is stationary. The droplets of the agent may be naturally evaporated. Further, the control device 22 may evaporate the droplets of the second hydrophobizing agent while being transported by the transport robot.

  The third processing example corresponds to the first processing example described above, and the fourth processing example corresponds to the second processing example described above. That is, the substrate W processed by the substrate processing apparatus 201 is, for example, the substrate W (see FIG. 7) on which the pattern P of the laminated film 32 is formed. When the first film 32a, the second film 32b, and the third film 32c are a film containing silicon, a film containing silicon, and a metal film, respectively (see FIG. 8), in the third processing example, for example, a silicon-based film A hydrophobizing agent or a metal hydrophobizing agent is used as the first hydrophobizing agent. When the first film 32a, the second film 32b, and the third film 32c are a film containing silicon, a film containing silicon, and a metal film, respectively (see FIG. 8), in the fourth processing example, for example, A metal hydrophobizing agent is used as the first hydrophobizing agent, and a silicon hydrophobizing agent is used as the second hydrophobizing agent. The same applies to other combinations of the first film 32a, the second film 32b, and the third film 32c.

  As described above, in the second embodiment, the hydrophobizing agent vapor is supplied to the substrate W in both the third processing example and the fourth processing example (the first hydrophobizing process and the second hydrophobizing process). processing). A part of the hydrophobizing agent vapor supplied to the substrate W changes into droplets and adheres to the substrate W. However, the hydrophobizing agent droplets evaporate in a short time and are removed from the substrate W. Therefore, it is not necessary to wash away the hydrophobizing agent with a solvent as in the first processing example and the second processing example. That is, the pre-drying rinsing process may not be performed. Thereby, the processing time of the substrate W can be shortened.

  In the fourth treatment example, after the first hydrophobic treatment, the second solvent rinse treatment is performed prior to the second hydrophobic treatment. When the first hydrophobizing treatment is finished, when the droplets of the first hydrophobizing agent evaporate from the substrate W and the substrate W is dried, the hydrophobicity of the substrate W is not sufficiently lowered. There is a risk of collapse. Therefore, the substrate W is prevented from drying by performing the second solvent rinsing process for supplying the solvent to the substrate W before the droplets of the first hydrophobizing agent are removed by evaporation. Thereafter, the vapor of the second hydrophobizing agent is supplied, whereby the solvent adhering to the substrate W is replaced with the second hydrophobizing agent, and the second hydrophobizing treatment is performed.

  In the third processing example and the fourth processing example, pure water is in contact with the substrate W until the substrate W is hydrophobized and then dried (from the end of the first hydrophobizing process to the end of the drying process). The state which does not do is kept. Therefore, when an amine having a hydrophobic group, which is an example of a metal hydrophobizing agent, is supplied to the substrate W including the metal film, the hydrophobicity of the substrate W is prevented from being significantly reduced. Thereby, collapse of the pattern P can be suppressed or prevented.

In addition, since the state in which pure water does not contact the substrate W is maintained until the substrate W is dried after being hydrophobized, the generation of watermarks can be suppressed or prevented.
Although the embodiments of the present invention have been described above, the present invention is not limited to the contents of the above-described embodiments, and various modifications can be made within the scope of the claims.

For example, in the first to fourth processing examples described above, the case where the solvent is supplied to the substrate W in the first solvent rinsing process, the second solvent rinsing process, and the pre-drying rinsing process has been described. The solvent vapor may be supplied if it is sufficiently dissolved in the liquid.
In the first to fourth processing examples, the first hydrophobizing process for supplying the first hydrophobizing agent to the substrate W after the first solvent rinsing process for supplying the solvent to the substrate W is performed. The case where it is performed was explained. However, when the pure water is dissolved in the first hydrophobizing agent and the activity does not decrease even when the first hydrophobizing agent contacts the pure water, a water rinsing process for supplying pure water to the substrate W is performed. After that, the first hydrophobizing treatment may be performed without performing the first solvent rinsing treatment.

  In the second processing example described above, the second solvent rinsing process for supplying the solvent to the substrate W is performed after the first hydrophobizing process and before the second hydrophobizing process. Explained. However, when the first hydrophobizing agent and the second hydrophobizing agent are easily mixed, the first hydrophobizing process for supplying the first hydrophobizing agent to the substrate W is performed without performing the second solvent rinsing process. After the breakage, a second hydrophobizing process for supplying the second hydrophobizing agent to the substrate W may be performed.

  In the first to fourth processing examples, the liquid or vapor of the hydrophobizing agent diluted to a certain concentration is supplied to the substrate W in the first hydrophobizing process and the second hydrophobizing process. Explained. However, the concentration of the hydrophobizing agent may be increased continuously or stepwise by the controller 22 controlling the opening degree of the flow rate adjusting valves 28 and 30 (see FIGS. 4 and 18). In this case, since the solvent adhering to the substrate W in the first hydrophobizing treatment and the second hydrophobizing treatment can be smoothly replaced with the hydrophobizing agent, the time for removing the solvent from the substrate W can be shortened.

  In the first to fourth processing examples, the case where the substrate W is processed while discharging the processing liquid from the chemical liquid nozzle 10 and the central axis nozzle 14 has been described. However, the substrate W may be processed by holding a liquid film of the processing liquid on the substrate W. Specifically, the processing liquid is discharged from the chemical nozzle 10 or the central axis nozzle 14 while rotating the substrate W at a low rotation speed of about 10 to 30 rpm by the spin chuck 2 or stopping the rotation of the substrate W. Then, after the liquid film of the processing liquid covering the upper surface of the substrate W is formed, the discharge of the processing liquid is stopped. Thereafter, the substrate W is processed with the liquid film of the processing liquid while the substrate W is rotated at the above-described low rotation speed or the rotation of the substrate W is stopped while the discharge of the processing liquid is stopped.

In the first to fourth processing examples, the case where pure water, which is an example of the rinsing liquid, is supplied to the substrate in the water rinsing process has been described. However, not only pure water, but also a rinsing liquid other than pure water may be supplied to the substrate.
In the first processing example to the fourth processing example, the case where the substrate W on which the pattern P of the laminated film 32 is formed has been described. However, the substrate W on which the single film pattern P is formed may be processed. For example, for the substrate W on which the pattern P of only the SiN film is formed, the silicon-based hydrophobizing agent having a long hydrophobic group and the silicon-based hydrophobizing agent having a short hydrophobic group as described above are used in the second processing example or the fourth processing. By being treated in the example, the SiN film can be sufficiently hydrophobized.

  In the second treatment example and the fourth treatment example, the hydrophobizing treatment is performed twice using the first hydrophobizing agent and the second hydrophobizing agent, but the hydrophobizing treatment is further performed using the third hydrophobizing agent. May be performed three times. For example, in the case of the combination of films shown in FIG. 10, a metal-based hydrophobizing agent is used as the first hydrophobizing agent to hydrophobize the metal film, and the second hydrophobizing agent is a silicon-based hydrophobic The hydrophobizing treatment of the SiN film is performed by using the agent I, and the hydrophobizing treatment of the SiN film is performed by using the silicon hydrophobizing agent II having a short hydrophobic group as the third hydrophobizing agent. Also good.

In the first to fourth processing examples, the case where the substrates W are processed one by one has been described. However, in the first processing example to the fourth processing example, a plurality of substrates W may be processed at once.
In addition, various design changes can be made within the scope of matters described in the claims.

1. Substrate processing apparatus 2. Spin chuck (substrate holding means, substrate drying means)
16 First hydrophobizing agent supply unit 17 Second hydrophobizing agent supply unit 18 Solvent valve (solvent supply means)
20 Rinsing liquid valve (rinsing liquid supply means)
22 Control device (control means)
32 laminated film 201 substrate processing apparatus 216 first hydrophobizing agent supply unit (hydrophobizing agent supplying means)
217 Second hydrophobizing agent supply unit (hydrophobizing agent supplying means)
P pattern S102 water rinsing step S103 first solvent rinsing step S104 first hydrophobizing step S105 pre-drying rinsing step S106 drying step S107 second solvent rinsing step S108 second hydrophobizing step S109 pre-drying rinsing step S110 drying step S204 first hydrophobic Step, first vapor supply step S205 drying step, evaporation step S207 second hydrophobization step, second vapor supply step S208 drying step, evaporation step W substrate

Claims (6)

A pattern of a laminated film including first and second films laminated so that one is positioned on the other protrudes from the surface, and the first and second films are different types of films, A substrate processing method for processing a substrate in which each of the first and second films contains silicon or metal,
A first solvent rinsing step of supplying a first solvent capable of dissolving the first hydrophobizing agent to the substrate;
After the first solvent rinsing step is performed, the first hydrophobizing agent is supplied to the substrate with the first solvent adhering to the substrate to hydrophobize the surface of the first film. A first hydrophobization step;
After the first hydrophobizing step is performed, a second solvent capable of dissolving the second hydrophobizing agent different from the first hydrophobizing agent and the first hydrophobizing agent is used as the first hydrophobizing agent. A second solvent rinsing step of supplying an agent to the substrate in a state where the agent is attached to the substrate;
After the second solvent rinsing step is performed, the second hydrophobizing agent is supplied to the substrate with the second solvent adhering to the substrate to hydrophobize the surface of the second film. A second hydrophobization step;
A drying step of drying the substrate after the second hydrophobization step is performed,
At least one of the first hydrophobization step and the second hydrophobization step was diluted with a diluting solvent capable of dissolving the first solvent and the second solvent, and diluted with the diluting solvent. Supplying the hydrophobizing agent to the substrate as the first hydrophobizing agent or the second hydrophobizing agent.   2. The substrate processing method according to claim 1, wherein the pattern is obtained by laminating the first and second films in the order of the first film and the second film from the side close to the surface of the substrate.   The substrate processing method according to claim 1, wherein the first film is a film containing a metal, and the second film is a film containing silicon.   The substrate processing method according to claim 1, wherein the first film is a film containing silicon, and the second film is a film containing silicon different from the first film. The first hydrophobizing step includes a first vapor supplying step of supplying vapor of the first hydrophobizing agent to the substrate;
The second hydrophobizing step includes a second vapor supplying step of supplying vapor of the second hydrophobizing agent to the substrate;
The said drying process is a substrate processing method as described in any one of Claims 1-4 including the evaporation process which evaporates the said 2nd hydrophobizing agent adhering to the said board | substrate. The diluting solvent has a smaller surface tension than water, and a solvent having a boiling point lower than that of water, the substrate processing method according to any one of claims 1-5.

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