15 (S4). By heating the SAM 13 on the side wall of the via hole 11 before attaching the intermolecular binder 15 to the SAM 13, the reactivity of the SAM 13 to the intermolecular binder 15 and the fixing properties of the SAM 13 with respect to the side wall of the via hole 11 (the insulating film 21) can be enhanced.

Further, the substrate W may be subjected to a heating processing (S5) between the application of the intermolecular binder 15 (S4) and the supply of the electroless plating solution 20 (S6). By heating the intermolecular binder 15 attached to the SAM 13 before supplying the electroless plating solution 20 into the via hole 11, the reactivity of the intermolecular binder 15 to the metal and the fixing properties of the intermolecular binder 15 with respect to the SAM 13 can be enhanced.

Furthermore, the substrate W may be subjected to a heating processing (S7) after the supply of the electroless plating solution 20 (S6) (particularly, after the plated metal is precipitated). In this case, the fixing properties among the insulating film 21, the SAM 13, the intermolecular binder 15 and the plated metal can be enhanced.

Each of the above-described heating processings (S3, S5 and S7) is not necessarily performed. For example, only a heating processing that can be expected to have a great effect may be performed.

Specific heating temperatures in the above-described heating processings (S3, S5 and S7) are appropriately determined depending on the purpose of each processing. For example, a heating processing for the purpose of increasing the fixing properties between the structures (the SAM 13, the intermolecular binder 15 and/or the plated metal) of the substrate W and a heating processing for the purpose of increasing the reactivity of the structures of the substrate W are typically different from each other in the optimum heating temperature. Further, each of the above-described heating processings (S3, S5 and S7) may include a plurality of heating processes. In the plurality of heating processes, the substrate W may be heated at the same temperature or at different temperatures. Any processing that has not been described above may be further performed.

Hereinafter, a specific example of the heating processing will be described.

FIG. 7 is a flowchart showing an example of the heating processing (see S3 in FIG. 6) performed between the processing of supplying the solution of the SAM 13 and the process of supplying the solution of the intermolecular binder 15.

In the example shown in FIG. 7, after the solution containing the components of the SAM 13 is supplied to the side wall of the via hole 11 (S11 in FIG. 7), the substrate W is heated at a first temperature (S12). By heating the SAM 13 on the side wall of the via hole 11 at the first temperature before attaching the intermolecular binder 15 to the SAM 13, the bonding between the side wall of the via hole 11 and the SAM 13 can be enhanced. However, in the present heating processing, a curing reaction such as cross-linking is not completed in the entire SAM 13.

Therefore, the “first temperature” is effective in promoting the enhancement of the bonding between the side wall of the via hole 11 and the SAM 13, but effective in suppressing the completion of the curing reaction such as cross-linking in the entire SAM 13. The “first temperature” may vary depending on the actual composition of the SAM 13 and the actual heating time. In the present example, the “first temperature” is lower than a “second temperature” (see S14) to be described later. For example, it is lower than 100° C.

Then, a part of the SAM 13 is removed from the side wall of the via hole 11 (S13). That is, after the SAM 13 is heated at the first temperature and before the intermolecular binder 15 is attached to the SAM 13, a part of the SAM 13 is removed from the side wall of the via hole 11. Accordingly, the SAM 13 formed on the side wall of the via hole 11 can be thin by removing the excessive SAM 13 from the substrate W.

A method of removing the SAM 13 from the side wall of the via hole 11 is not limited. For example, an organic solution may be supplied to the SAM 13 on the side wall of the via hole 11 and a part of the SAM 13 having a low degree of fixing to the insulating film 21 (including the solution of the SAM 13) may be washed away with the organic solution.

Thereafter, the substrate W is heated at the second temperature (S14). By heating the SAM 13 on the side wall of the via hole 11 after removing the part of the SAM 13 from the side wall of the via hole 11 and before attaching the intermolecular binder 15 to the SAM 13, the reactivity of the SAM 13 to the intermolecular binder 15 can be increased. However, in the present heating process, a curing reaction such as cross-linking is not completed in the entire SAM 13.

Therefore, the “second temperature” is effective in increasing the reactivity of the SAM 13 to the intermolecular binder 15, but effective in suppressing the completion of the curing reaction such as cross-linking in the entire SAM 13. For example, a temperature at which a cutoff (i.e., cleavage) of a covalent bond in constituent molecules of the SAM 13 (particularly, a functional group that reacts with the intermolecular binder 15) can be urged may be set as the “second temperature”. The “second temperature” may vary depending on the actual composition of the SAM 13 and the actual heating time. In the present example, the “second temperature” is higher than the “first temperature” (see S12). For example, it is higher than 100° C. and lower than 250° C.

Then, the solution of the intermolecular binder 15 is supplied onto the SAM 13 that partitions the via hole 11 (S15). As a result, the intermolecular binder 15 is attached to the SAM 13 whose reactivity has been increased, and, thus, the intermolecular binder 15 can be firmly bonded to the SAM 13.

As described above, according to the example of the heating processing shown in FIG. 7, the SAM 13 can be firmly bonded to the insulating film 21, and the intermolecular binder 15 can also be firmly bonded to the SAM 13. Further, the thickness of the SAM 13 in the form of the thin film is adjusted with high precision by performing the processing (S13) of removing the part of the SAM 13 between the heating processing at the first temperature (S12) and the heating processing at the second temperature (S14).

FIG. 8 is a flowchart showing an example of the heating processing (see S5 in FIG. 6) performed between the processing of supplying the solution of the intermolecular binder 15 and the processing of supplying the electroless plating solution 20.

In the example shown in FIG. 8, after the solution containing the components of the intermolecular binder 15 is supplied onto the SAM 13 (S21 in FIG. 8), the substrate W is heated at a third temperature (S22). By heating the intermolecular binder 15 attached to the SAM 13 at the third temperature before supplying the electroless plating solution 20 into the via hole 11, the bonding between the intermolecular binder 15 and the SAM 13 can be enhanced. However, in the present heating processing, a curing reaction such as cross-linking is not completed in the entire intermolecular binder 15.

Therefore, the “third temperature” is effective in promoting the enhancement of the bonding between the SAM 13 and the intermolecular binder 15, but effective in suppressing the completion of the curing reaction such as cross-linking in the entire intermolecular binder 15. The “third temperature” may vary depending on the actual composition of the intermolecular binder 15 and the actual heating time. In the present example, the “third temperature” is lower than a “fourth temperature” (see S24) to be described later. For example, it is lower than 100° C.

Then, a part of the intermolecular binder 15 is removed from the SAM 13 (S23). That is, after the intermolecular binder 15 is heated at the third temperature and before the electroless plating solution 20 is supplied into the via hole 11, a part of the intermolecular binder 15 is removed from the SAM 13. Accordingly, the intermolecular binder 15 formed on the SAM 13 can be thin by removing the excessive intermolecular binder 15 from the substrate W.

A method of removing the intermolecular binder 15 from the SAM 13 is not limited. For example, an organic solution may be supplied to the intermolecular binder 15 on the SAM 13 and a part of the intermolecular binder 15 having a low degree of fixing to the SAM 13 (including the solution of the intermolecular binder 15) may be washed away with the organic solution.

Thereafter, the substrate W is heated at the fourth temperature (S24). By heating the intermolecular binder 15 on the SAM 13 after removing the part of the intermolecular binder 15 from the SAM 13 and before supplying the electroless plating solution 20 into the via hole 11, the bonding of the intermolecular binder 15 to the SAM 13 can be enhanced. Also, the reactivity of the intermolecular binder 15 to the metal buried in the via hole 11 may be increased by the present heating processing. However, in the present heating processing, the reactivity of the intermolecular binder 15 to the plated metal is not greatly degraded.

Therefore, the “fourth temperature” is effective in increasing the reactivity of the intermolecular binder 15 to the SAM 13, but effective in suppressing the great degradation of the reactivity of the intermolecular binder 15 to the plated metal. The “fourth temperature” may vary depending on the actual composition of the intermolecular binder 15 and the actual heating time. In the present example, the “fourth temperature” is higher than the “third temperature” (see S22). For example, it is in the range of from 250° C. to 300° C.

Then, the electroless plating solution 20 is supplied into the via hole 11 (S25). As a result, in the via hole 11, the metal is bonded to the intermolecular binder 15 while the metal is gradually deposited. Therefore, the metal buried in the via hole 11 can be firmly fixed to the SAM 13 via the intermolecular binder 15.

As described above, according to the example of heating processing shown in FIG. 8, the intermolecular binder 15 can be firmly bonded to the SAM 13, and the metal buried in the via hole 11 can also be firmly bonded to the intermolecular binder 15. Further, the thickness of the intermolecular binder 15 in the form of the thin film is adjusted with high precision by performing the processing (S23) of removing the part of the intermolecular binder 15 between the heating processing at the third temperature (S22) and the heating processing at the fourth temperature (S24).

FIG. 9 is a flowchart showing another example of the heating processing (see S5 in FIG. 6) performed between the processing of supplying the solution of the intermolecular binder 15 and the processing of supplying the electroless plating solution 20.

In the example shown in FIG. 9, after the solution containing the components of the intermolecular binder 15 is supplied onto the SAM 13 (S31 in FIG. 9), the substrate W is heated at a fifth temperature (S32). By heating the intermolecular binder 15 attached to the SAM 13 at the fifth temperature before supplying the electroless plating solution 20 into the via hole 11, the bonding between the intermolecular binder 15 and the SAM 13 can be enhanced. Also, particularly, a part of the intermolecular binder 15 on the SAM 13 with a desired thickness can be firmly fixed to the intermolecular binder 15 by the present heating processing. However, in the present heating processing, the reactivity of the intermolecular binder 15 to the plated metal is not greatly degraded.

Therefore, the “fifth temperature” is effective in promoting the enhancement of the bonding between the SAM 13 and the intermolecular binder 15 and fixing a part of the intermolecular binder 15 remaining on the SAM 13 to the SAM 13. However, the “fifth temperature” is effective in suppressing the great degradation of the reactivity of the intermolecular binder 15 to the plated metal. The “fifth temperature” may vary depending on the actual composition of the intermolecular binder 15 and the actual heating time. In the present example, the “fifth temperature” is higher than the “third temperature” (see S22 in FIG. 8). For example, it is in the range of from 250° C. to 300° C.

Then, a part of the intermolecular binder 15 is removed from the SAM 13 (S33). That is, after the intermolecular binder 15 is heated at the fifth temperature and before the electroless plating solution 20 is supplied into the via hole 11, the part of the intermolecular binder 15 is removed from the SAM 13. Accordingly, the excessive intermolecular binder 15 can be removed from the substrate W. A method of removing the intermolecular binder 15 in the present processing can be performed in the same manner as in the example (particularly, process S23) shown in FIG. 8.

Then, the electroless plating solution 20 is supplied into the via hole 11 (S34). As a result, in the via hole 11, the metal is bonded to the intermolecular binder 15 while the metal is gradually deposited. Therefore, the metal buried in the via hole 11 can be firmly fixed to the SAM 13 via the intermolecular binder 15.

As described above, according to the example of the heating processing shown in FIG. 9, the intermolecular binder 15 can be firmly bonded to the SAM 13, and the metal buried in the via hole 11 can also be firmly bonded to the intermolecular binder 15. Further, the intermolecular binder 15 is subjected to the heating processing (S32) only once, and, thus, the processing flow can be simplified and the total processing time can be shortened as compared to the case where the intermolecular binder 15 is subjected to the plurality of heating processings (see FIG. 8).

The processing flow shown in FIG. 7 may or may not be combined with the processing flow shown in FIG. 8 or the processing flow shown in FIG. 9, and may be combined with another processing flow. Likewise, each of the processing flow shown in FIG. 8 and the processing flow shown in FIG. 9 may be combined with a processing flow different from the processing flow shown in FIG. 7.

[Example of Composition of Self-Assembled Monolayer and Intermolecular Binder]

A specific composition of each of the SAM 13 and the intermolecular binder 15 is basically not limited, but is selected in comprehensive consideration of various required properties. In particular, the composition of the SAM 13 of the present exemplary embodiment is determined in consideration of the function as the diffusion barrier layer, the good bonding properties to the insulating film 21 and the intermolecular binder 15, and the secured exposure of the cap layer 14. Meanwhile, the composition of the intermolecular binder 15 is determined in consideration of the good bonding properties to the SAM 13 and the plated metal, and the secured exposure of the cap layer 14.

For example, a silanol-based organic film may be used as the SAM 13. By using an organic film having a hydroxy group as the SAM 13, the SAM 13 may be dehydration-synthesized to the side wall of the via hole 11 (the insulating film 21) and the intermolecular binder 15. For example, the silanol-based SAM 13 may be formed on the side wall of the via hole 11 formed of a silicon-containing material.

Meanwhile, for example, a compound (e.g., a silane coupling agent) having both a functional group that reacts with and is bonded to an organic material (i.e., the SAM 13) and a functional group that reacts with and is bonded to an inorganic material (i.e., the plated metal) in a molecule may be used as the intermolecular binder 15. Examples of the functional group that reacts with and is bonded to the organic material may include a vinyl group, an epoxy group, an amino group, a methacryl group and a mercapto group. Also, the functional group that reacts with and is bonded to the inorganic material may be a functional group that produces silanol by reaction with water (including moisture), and examples thereof may include an alkoxy group (e.g., a methoxy group and an ethoxy group), an acetoxy group, and a chloro atom. Alternatively, a compound having a ligand (e.g., an amino group or a thiol group) that is coordinate-bonded to a metal may be used as the intermolecular binder 15. Examples of the compound having these functional groups may include triazine.

FIG. 10 is a structural formula showing an example of the molecular structure of the triazine that can be used as the intermolecular binder 15. A compound forming the intermolecular binder 15 has an organic reactive group 28 (a hydroxy group (—OH) in FIG. 10) that can be bonded to the SAM 13 formed of the organic material. Meanwhile, the compound forming the intermolecular binder 15 has an inorganic reactive group 29 (a thiol group (—SH) in FIG. 10) that can be bonded to the plated metal formed of the inorganic material. If the intermolecular binder 15 contains a compound having a thiol group, the thiol group of the intermolecular binder 15 is self-assembled on the surface of the plated metal (copper in the present example).

[Substrate Liquid Processing Apparatus]

Hereinafter, an example of a substrate liquid processing apparatus configured to perform the above-described substrate liquid processing method will be described.

FIG. 11 is a diagram schematically illustrating an example of a SAM processing unit 30a including a SAM solution supply unit 31. A specific configuration of each component of the SAM solution supply unit 31 is not limited. Each component of the SAM solution supply unit 31 is simply illustrated in FIG. 11.

The SAM solution supply unit 31 is configured to supply the organic solution containing the constituent molecules of the SAM 13 to the substrate W to form the SAM 13 on the side walls of the via hole 11 and the trench 12. The illustrated SAM solution supply unit 31 includes a first discharge member 32 configured to be moved by a first discharge driving unit 34, a first substrate holder 35, a first cup structure 36 and a first inert gas supply 37. Particularly, the first discharge member 32, the first discharge driving unit 34, the first substrate holder 35 and the first cup structure 36 are provided inside a first processing chamber 39.

The first substrate holder 35 is configured to hold the substrate W rotatably. The illustrated first substrate holder 35 attracts and holds a rear surface of the substrate W. A specific method of holding the substrate W is not limited. The first discharge member 32 includes at least a nozzle (not shown) configured to discharge the organic solution containing the constituent molecules of the SAM 13. The first discharge member 32 may be configured to discharge another fluid. For example, a cleaning solution for cleaning the substrate W or a rinse solution for rinsing the substrate W may be discharged from the first discharge member 32. When a plurality of kinds of fluids (e.g., a plurality of kinds of liquids) is discharged from the first discharge member 32, the first discharge member 32 may discharge two or more kinds of fluids from a common nozzle or may include two or more nozzles for discharging different kinds of fluids. Further, a fluid (including the organic solution of the SAM 13) discharged from the first discharge member 32 is supplied from a non-illustrated fluid source to the first discharge member 32 through a flow path provided in the first discharge driving unit 34.

The first cup structure 36 having an annular planar shape is provided to surround the substrate W held by the first substrate holder 35. The first cup structure 36 receives a liquid scattered from the substrate W and guides the received liquid into a drain duct (not shown) or rectifies a gas flow to suppress diffusion of a gas around the substrate W. A specific configuration of the first cup structure 36 is not limited. For example, the first cup structure 36 may have a cup for mainly guiding the liquid and a cup for mainly rectifying the gas flow separately.

The first inert gas supply 37 is configured to supply an inert gas (e.g., nitrogen) into the first processing chamber 39. The first processing chamber 39 is basically sealed, and, thus, outside air cannot be introduced into the first processing chamber 39. The first processing chamber 39 does not necessarily require complete airtightness, and just needs to be sealed to effectively suppress the introduction of the outside air into the first processing chamber 39 (particularly, introduction of the outside air to around the substrate W held by the first substrate holder 35).

In the above-described SAM processing unit 30a, the organic solution containing the constituent molecules of the SAM 13 is supplied to the substrate W. That is, the substrate W is carried into the first processing chamber 39, and in a state where the substrate W is held by the first substrate holder 35, the organic solution is discharged from the first discharge member 32 toward the processing surface (upper surface) of the substrate W. In this case, the organic solution containing the constituent molecules of the SAM 13 may be supplied to the processing surface of the substrate W while the substrate W is rotated by the first substrate holder 35.

A landing position of the liquid discharged from the first discharge member 32 on the processing surface of the substrate W is not limited. The first discharge member 32 may allow the organic solution to land on the center of the processing surface of the substrate W (i.e., on a central axis of rotation of the substrate W rotated by the first substrate holder 35), or to land at a position deviated from the center of the processing surface of the substrate W.

FIG. 12 is a diagram schematically illustrating an example of an intermolecular binder processing unit 30b including an intermolecular binder supply unit 41. A specific configuration of each component of the intermolecular binder supply unit 41 is not limited. Each component of the intermolecular binder supply unit 41 is simply illustrated in FIG. 12.

The intermolecular binder supply unit 41 is configured to supply the solution containing constituent molecules of the intermolecular binder 15 to the substrate W to form the layer of the intermolecular binder 15 on the SAM 13. The illustrated intermolecular binder supply unit 41 includes a second discharge member 42 configured to be moved by a second discharge driving unit 44, a second substrate holder 45, a second cup structure 46 and a second inert gas supply 47. Particularly, the second discharge member 42, the second discharge driving unit 44, the second substrate holder 45 and the second cup structure 46 are provided inside a second processing chamber 49.

The second discharge member 42 includes at least a nozzle (not shown) configured to discharge the solution containing the constituent molecules of the intermolecular binder 15. Like the first discharge member 32, the second discharge member 42 may be configured to discharge another fluid. Further, a fluid (including the solution of the intermolecular binder 15) discharged from the second discharge member 42 is supplied from a non-illustrated fluid source to the second discharge member 42 through a flow path provided in the second discharge driving unit 44. The second substrate holder 45, the second cup structure 46, the second inert gas supply 47 and the second processing chamber 49 have the same configuration and effect as the above-described first substrate holder 35, first cup structure 36, first inert gas supply 37 and first processing chamber 39, respectively.

In the above-described intermolecular binder processing unit 30b, the solution containing the constituent molecules of the intermolecular binder 15 is supplied to the substrate W. That is, the substrate W including the SAM 13 is carried into the second processing chamber 49, and in a state where the substrate W is held by the second substrate holder 45, the solution is discharged from the second discharge member 42 toward the processing surface of the substrate W. In this case, the solution containing the constituent molecules of the intermolecular binder 15 may be supplied to the processing surface of the substrate W while the substrate W is rotated by the second substrate holder 45.

A landing position of the liquid discharged from the second discharge member 42 on the processing surface of the substrate W is not limited. The second discharge member 42 may allow the solution containing the constituent molecules of the intermolecular binder 15 to land on the center of the processing surface of the substrate W or to land at a position deviated from the center of the processing surface of the substrate W.

FIG. 13 is a diagram schematically illustrating an example of a plating processing unit 30c including an electroless plating solution supply unit 51. A specific configuration of each component of the electroless plating solution supply unit 51 is not limited. Each component of the electroless plating solution supply unit 51 is simply illustrated in FIG. 13.

The electroless plating solution supply unit 51 is configured to supply the electroless plating solution 20 to the via hole 11 of the substrate W to precipitate the metal in the via hole 11. The illustrated electroless plating solution supply unit 51 includes a third discharge member 52 configured to be moved by a third discharge driving unit 54, a third substrate holder 55, a third cup structure 56, a third inert gas supply 57 and a first heating device 58 equipped with a first heater 58a. The third discharge member 52, the third discharge driving unit 54, the third substrate holder 55, the third cup structure 56 and the first heating device 58 are provided inside a third processing chamber 59.

The third discharge member 52 includes at least a nozzle (not shown) configured to discharge the electroless plating solution 20. Like the first discharge member 32, the third discharge member 52 may be configured to discharge another fluid. A fluid (including the electroless plating solution 20) discharged from the third discharge member 52 is supplied from a non-illustrated fluid source to the third discharge member 52 through a flow path provided in the third discharge driving unit 54. The third substrate holder 55, the third cup structure 56, the third inert gas supply 57 and the third processing chamber 59 have the same configuration and effect as the above-described first substrate holder 35, first cup structure 36, first inert gas supply 37 and first processing chamber 39, respectively.

The first heating device 58 can be moved up and down by a non-illustrated driving mechanism. For example, when the substrate W is heated, the first heating device 58 is located at a lower position close to the substrate W. When the substrate W is not heated, the first heating device 58 is located at an upper position away from the substrate W. While the third discharge member 52 is located above the substrate W, the first heating device 58 is located at a height position where it does not contact nor collide with the third discharge member 52 and the third discharge driving unit 54.

In the illustrated example, the first heating device 58 serving as a top plate covering the substrate W held by the third substrate holder 55 from above and the third discharge member 52 configured to supply the electroless plating solution 20 to the substrate W are provided separately. However, the nozzle configured to discharge the electroless plating solution 20 toward the substrate W may also be integrally provided with the top plate. For example, a liquid guide hole (not shown) formed through the first heating device 58 at the center of the first heating device 58 (i.e., at a position facing the center of the substrate W in a height direction) may be used as the nozzle configured to discharge the electroless plating solution 20 toward the substrate W. In this case, although not illustrated in the drawings, a plating solution supply path may be connected to the liquid guide hole via a valve, and the electroless plating solution 20 may be supplied to the substrate W from a bottom opening of the liquid guide hole while the valve is opened.

In the above-described plating processing unit 30c, the electroless plating solution 20 is supplied to the substrate W and the plated metal (copper in the present example) is buried in the via hole 11. That is, the substrate W including the SAM 13 and the intermolecular binder 15 is carried into the third processing chamber 59, and in a state where the substrate W is held by the third substrate holder 55, the electroless plating solution 20 is discharged from the third discharge member 52 toward the processing surface of the substrate W. In this case, the electroless plating solution 20 may be supplied to the processing surface of the substrate W while the substrate W is rotated by the third substrate holder 55.

A landing position of the liquid discharged from the third discharge member 52 on the processing surface of the substrate W is not limited. The third discharge member 52 may allow the electroless plating solution 20 to land on the center of the processing surface of the substrate W or to land at a position deviated from the center of the processing surface of the substrate W.

Then, the entire processing surface of the substrate W is maintained in a state of being supplied with the electroless plating solution 20, and with the elapse of time, the metal is deposited and grows in the via hole 11. As a result, the metal is buried in the via hole 11 to form the via wiring 24 in the via hole 11. In this case, the electroless plating solution 20 on the substrate W may be heated by the first heating device 58 to promote the deposition of the metal. For example, the electroless plating solution 20 on the substrate W can be heated by locating the first heating device 58 at the lower position to allow the first heater 58a in a heating state to approach the processing surface of the substrate W.

Thereafter, the metal (wiring) is also buried in the trench 12. The metal buried in the trench 12 is physically and electrically connected to the via wiring 24 in the via hole 11. The metal can be buried in the trench 12 by any method. For example, the plated metal can be buried in the trench 12 by a known electroless plating method or electroplating method.

The substrate W in which the metal is buried in the via hole 11 and the trench 12 as described above is transferred from the plating processing unit 30c to a heating processing unit. The substrate W in which the metal is buried in the via hole 11 and the trench 12 may be subjected to a rinse processing, a drying processing and other processings in the plating processing unit 30c before being transferred to the heating processing unit.

FIG. 14 is a diagram schematically illustrating an example of a removal processing unit 30d including a removal solution supply unit 61. A specific configuration of each component of the removal solution supply unit 61 is not limited. Each component of the removal solution supply unit 61 is simply illustrated in FIG. 14.

The removal solution supply unit 61 is configured to supply the removal solution (organic solution or the like) to the substrate W and remove unnecessary solutions (e.g., the above-described solution of the SAM 13 and solution of the intermolecular binder 15) from the substrate W (the via hole 11) together with the removal solution. A composition of the removal solution is appropriately determined depending on the solution to be removed. The illustrated removal solution supply unit 61 includes a fourth discharge member 62 configured to be moved by a fourth discharge driving unit 64, a fourth substrate holder 65, a fourth cup structure 66 and a fourth inert gas supply 67. The fourth discharge member 62, the fourth discharge driving unit 64, the fourth substrate holder 65 and the fourth cup structure 66 are provided inside a fourth processing chamber 69.

The fourth discharge member 62 includes at least a nozzle (not shown) configured to discharge the removal solution. Like the first discharge member 32, the fourth discharge member 62 may be configured to discharge another fluid. Further, a fluid (including the removal solution) discharged from the fourth discharge member 62 is supplied from a non-illustrated fluid source to the fourth discharge member 62 through a flow path provided in the fourth discharge driving unit 64. The fourth substrate holder 65, the fourth cup structure 66, the fourth inert gas supply 67 and the fourth processing chamber 69 have the same configuration and effect as the above-described first substrate holder 35, first cup structure 36, first inert gas supply 37 and first processing chamber 39, respectively.

In the above-described removal processing unit 30d, the unnecessary solutions (e.g., the above-described solution of the SAM 13 and solution of the intermolecular binder 15) are removed from the substrate W. In this case, the removal solution may be supplied to the processing surface of the substrate W while the substrate W is rotated by the fourth substrate holder 65.

A landing position of the liquid discharged from the fourth discharge member 62 on the processing surface of the substrate W is not limited. The fourth discharge member 62 may allow the removal solution to land on the center of the processing surface of the substrate W or to land at a position deviated from the center of the processing surface of the substrate W.

FIG. 15 is a diagram schematically illustrating an example of a heating processing unit 30e including a heating unit 75. A specific configuration of each component of the heating unit 75