Substrate processing apparatus and substrate processing method

Abstract

To provide a technique that can properly hydrophobize the entire surface of a substrate in a shorter time.SOLUTION: A substrate processing apparatus includes a substrate holding part 2, at least one central nozzle 3, a first hydrophobic tube 31h, a first hydrophobic control valve 32h, at least one peripheral nozzle 4, a second hydrophobic tube 41h, a second hydrophobic control valve 42h and a control part 9. The central nozzle 3 discharges fluid toward the central part of a main surface of the substrate W held by the substrate holding part 2. The first hydrophobic control valve 32h adjusts the first hydrophobic flow rate Fh1 of the hydrophobic solution flowing in the first hydrophobic tube 31h. The peripheral nozzle 4 discharges fluid toward the periphery of the main surface of the substrate W. The second hydrophobic control valve 42h adjusts the second hydrophobic flow rate Fh2 of the hydrophobic solution flowing in the second hydrophobic tube 41h. The control part 9 adjusts the hydrophobic flow rate ratio of the first hydrophobic flow rate Fh1 to the second hydrophobic flow rate Fh2. The control part 9 makes the hydrophobic flow rate ratio in the first period higher than the hydrophobic flow rate ratio in the second period after the first period.SELECTED DRAWING: Figure 2

Description

Technical Field

[0001] The present disclosure relates to a substrate processing apparatus and a substrate processing method.

Background Art

[0002] Conventionally, a substrate processing apparatus that supplies a processing liquid to a substrate to process the substrate has been proposed. After performing liquid processing on the substrate using the processing liquid, the substrate processing apparatus supplies a highly volatile rinse liquid to the substrate and then performs a drying process of evaporating the rinse liquid to dry the substrate. In this drying process, there is a possibility that the pattern on the substrate may collapse due to the surface tension of the rinse liquid.

[0003] A substrate processing apparatus that can suppress the occurrence of collapse of the pattern on this substrate has also been proposed (for example, Patent Documents 1 and 2). In Patent Documents 1 and 2, the substrate processing apparatus supplies a hydrophobizing liquid to the surface of the substrate to hydrophobize the surface of the substrate, and then supplies a highly volatile rinse liquid to the surface of the substrate. Then, the substrate processing apparatus evaporates the rinse liquid to dry the substrate. According to this, since the surface of the substrate is hydrophobized, the contact angle of the liquid surface of the rinse liquid between the patterns becomes large, and the collapse stress on the pattern due to the surface tension can be reduced. Therefore, the substrate can be dried while suppressing the occurrence of collapse of the pattern.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] When a hydrophobic solution is applied to the center of a rotating substrate, there is a problem in that the peripheral areas of the substrate are not sufficiently hydrophobic. This is thought to be because, as the hydrophobic solution applied to the center of the substrate spreads along the main surface of the substrate, it reacts with the moisture in the internal space of the chamber, causing the hydrophobic solution to become inactive. If the hydrophobic solution is inactive by the time it reaches the peripheral areas of the substrate, even if the hydrophobic solution is continuously supplied to the substrate for a long period of time, the peripheral areas of the substrate cannot be sufficiently hydrophobic. Furthermore, it is also desirable to hydrophobize the substrate in a shorter processing time.

[0006] Therefore, the purpose of this disclosure is to provide a technology that can hydrophobize the entire surface of a substrate more appropriately in a shorter amount of time. [Means for solving the problem]

[0007] The first embodiment is a substrate processing apparatus comprising: a substrate holding unit for holding and rotating a substrate; at least one central nozzle for discharging fluid toward the center of the main surface of the substrate held by the substrate holding unit; a first hydrophobic pipe for supplying a hydrophobic liquid as the fluid to the central nozzle; a first hydrophobic adjustment valve for adjusting a first hydrophobic flow rate of the hydrophobic liquid flowing through the first hydrophobic pipe; at least one peripheral nozzle for discharging fluid toward the peripheral edge of the main surface of the substrate held by the substrate holding unit; and the fluid as The substrate comprises a second hydrophobic pipe for supplying the hydrophobic solution to the peripheral nozzle, a second hydrophobic control valve for adjusting the second hydrophobic flow rate of the hydrophobic solution flowing through the second hydrophobic pipe, and a control unit that controls the first hydrophobic control valve and the second hydrophobic control valve to adjust the hydrophobic flow rate ratio of the first hydrophobic flow rate to the second hydrophobic flow rate, wherein the control unit makes the hydrophobic flow rate ratio during the first period of the hydrophobic treatment period for supplying the hydrophobic solution to the main surface of the substrate higher than the hydrophobic flow rate ratio during the second period following the first period of the hydrophobic treatment period.

[0008] A second embodiment is a substrate processing apparatus according to the first embodiment, wherein the control unit controls the first hydrophobic control valve and the second hydrophobic control valve to make the first hydrophobic flow rate in the first period greater than the second hydrophobic flow rate in the first period, and the first hydrophobic flow rate in the second period less than the second hydrophobic flow rate in the second period.

[0009] A third embodiment is a substrate processing apparatus according to the first or second embodiment, wherein the control unit controls the first hydrophobic control valve and the second hydrophobic control valve to make the first hydrophobic flow rate in the first period greater than the first hydrophobic flow rate in the second period, and the second hydrophobic flow rate in the first period less than the second hydrophobic flow rate in the second period.

[0010] A fourth embodiment is a substrate processing apparatus according to the third embodiment, wherein the control unit controls the first hydrophobic regulating valve and the second hydrophobic regulating valve to make the sum of the first hydrophobic flow rate and the second hydrophobic flow rate in the first period equal to the sum of the first hydrophobic flow rate and the second hydrophobic flow rate in the second period.

[0011] The fifth embodiment is a substrate processing apparatus according to any one of the first to fourth embodiments, wherein the second period is longer than the first period.

[0012] The sixth embodiment is a substrate processing apparatus according to any one of the first to fifth embodiments, wherein the rotational speed of the substrate during the second period is lower than the rotational speed of the substrate during the first period.

[0013] The seventh embodiment is a substrate processing apparatus according to any one of the first to sixth embodiments, wherein the peripheral nozzle is a fixed nozzle and, in a plan view, discharges the hydrophobic liquid in a direction along the rotational direction of the substrate.

[0014] The eighth aspect is a substrate processing apparatus according to any one of the first to sixth aspects, further comprising a nozzle moving mechanism for moving the peripheral nozzle between a peripheral processing position facing the peripheral edge of the main surface of the substrate and a peripheral standby position radially outward from the substrate.

[0015] The ninth embodiment is a substrate processing apparatus according to any one of the first to eighth embodiments, further comprising: a first solvent pipe connected to the at least one central nozzle for supplying the at least one central nozzle with an organic solvent as the fluid; a first solvent control valve interposed in the first solvent pipe for adjusting the first solvent flow rate of the organic solvent flowing through the first solvent pipe; a second solvent pipe connected to the at least one peripheral nozzle for supplying the at least one peripheral nozzle with the organic solvent as the fluid; and a second solvent control valve interposed in the second solvent pipe for adjusting the second solvent flow rate of the organic solvent flowing through the second solvent pipe, wherein the control unit controls the first solvent control valve and the second solvent control valve to adjust the solvent flow rate ratio of the first solvent flow rate to the second solvent flow rate, so that the solvent flow rate ratio during the first solvent period of the solvent processing period for supplying the organic solvent to the substrate is higher than the solvent flow rate ratio during the second solvent period of the solvent processing period which is later than the first solvent period.

[0016] The tenth aspect is a substrate processing apparatus according to the ninth aspect, wherein the sum of the first hydrophobic flow rate and the second hydrophobic flow rate is smaller than the sum of the first solvent flow rate and the second solvent flow rate.

[0017] The eleventh embodiment is a substrate processing apparatus according to any one of the first to tenth embodiments, further comprising: a first gas pipe connected to the at least one central nozzle for supplying the at least one central nozzle with an inert gas as the fluid; a first gas control valve interposed in the first gas pipe for adjusting the first gas flow rate of the inert gas flowing through the first gas pipe; a second gas pipe connected to the at least one peripheral nozzle for supplying the at least one peripheral nozzle with an inert gas as the fluid; and a second gas control valve interposed in the second gas pipe for adjusting the second gas flow rate of the inert gas flowing through the second gas pipe.

[0018] The twelfth embodiment is a substrate processing apparatus according to the eleventh embodiment, wherein the control unit controls the opening degree of the first gas control valve and the second gas control valve to a constant value during a gas treatment period in which an inert gas is supplied to the substrate.

[0019] A thirteenth aspect is a substrate processing method comprising: (a) a step of holding a substrate; and (b) a step of rotating the substrate while a central nozzle discharges a hydrophobic liquid toward the central part of the main surface of the substrate, and a peripheral nozzle discharges the hydrophobic liquid toward the peripheral part of the main surface of the substrate, wherein in step (b), the hydrophobic flow rate ratio of the first hydrophobic flow rate of the hydrophobic liquid deposited on the central part of the main surface of the substrate to the second hydrophobic flow rate of the hydrophobic liquid deposited on the peripheral part of the main surface of the substrate is made smaller in the second period following the first period than in the first period. [Effects of the Invention]

[0020] According to the 1st, 10th, and 13th aspects, in the first period, the hydrophobic flow rate ratio is high. Therefore, in the first period, the hydrophobized liquid lands on the central part of the substrate at a relatively large flow rate. Thus, even if there is a processing liquid on the main surface of the substrate, the processing liquid can be more quickly pushed out from the central part to the radial outer side. Therefore, the processing liquid at the central part of the substrate can be replaced by the hydrophobized liquid in a short time. In other words, the processing liquid at the central part of the substrate can be replaced by the hydrophobized liquid while reducing the usage amount of the hydrophobized liquid. Also, the hydrophobized liquid can be made to act more quickly on the central part of the main surface of the substrate. Therefore, the central part of the substrate can be hydrophobized more effectively.

[0021] On the other hand, since the hydrophobized liquid reacts with moisture in the air and becomes deactivated, the hydrophobized liquid that lands on the central part of the substrate may become deactivated when reaching the peripheral part of the substrate. For this reason, the hydrophobized liquid does not act effectively on the periphery of the substrate. Also, since the flow rate of the hydrophobized liquid discharged toward the peripheral part of the substrate is relatively small, the peripheral part is not hydrophobized much.

[0022] In the second period, the hydrophobic flow rate ratio is low. Therefore, in the second period, the hydrophobized liquid is supplied to the peripheral part at a relatively large flow rate. For this reason, the hydrophobized liquid acts effectively on the peripheral part of the substrate, and the peripheral part of the substrate can be effectively hydrophobized.

[0023] According to the second aspect, in the first period, while the processing liquid on the main surface of the substrate can be more quickly pushed out to the radial outer side of the substrate, the central part of the main surface of the substrate can be hydrophobized more quickly, and in the second period, the peripheral part of the main surface of the substrate can be hydrophobized more quickly.

[0024] According to the third aspect, the difference between the sum of the first hydrophobic flow rate and the second hydrophobic flow rate in the first period and the sum of the first hydrophobic flow rate and the second hydrophobic flow rate in the second period can be reduced.

[0025] According to the fourth aspect, it is possible to eliminate the difference between the sum of the first hydrophobic flow rate and the second hydrophobic flow rate in the first period and the sum of the first hydrophobic flow rate and the second hydrophobic flow rate in the second period.

[0026] According to the fifth aspect, the peripheral portion of the substrate can be more appropriately hydrophobized.

[0027] According to the sixth aspect, the peripheral portion of the substrate can be more appropriately hydrophobized.

[0028] According to the seventh aspect, it is possible to suppress the liquid splash of the hydrophobizing liquid on the main surface of the substrate.

[0029] According to the eighth aspect, the hydrophobizing liquid can be discharged to the peripheral portion of the substrate at a position close to the main surface of the substrate.

[0030] According to the ninth aspect, in the first solvent period, the solvent flow rate ratio is high. Therefore, in the first solvent period, the organic solvent lands on the central portion of the substrate at a relatively large flow rate. Thus, the hydrophobizing liquid on the main surface of the substrate can be more quickly pushed from the central portion to the radially outer side. Therefore, the hydrophobizing liquid can be more quickly replaced by the organic solvent at the central portion of the substrate. Moreover, since the organic solvent also lands on the peripheral portion of the main surface of the substrate, the entire main surface of the substrate can be more appropriately covered with the organic solvent.

[0031] In the second solvent period, the organic solvent lands on the peripheral portion of the substrate at a relatively large flow rate. Therefore, the hydrophobizing liquid at the peripheral portion of the substrate can be more effectively replaced by the organic solvent.

[0032] According to the eleventh aspect, the substrate can be quickly dried.

[0033] According to the twelfth aspect, the processing load of the control unit can be reduced.

Brief Description of the Drawings

[0035] The embodiments will be described in detail below with reference to the drawings. Note that, for the purpose of ease of understanding, the dimensions and number of parts in the drawings are exaggerated or simplified as needed. Also, parts with similar configurations and functions are denoted by the same reference numerals, and redundant explanations are omitted in the following description.

[0036] Furthermore, in the following explanations, similar components will be denoted by the same symbols, and their names and functions will also be the same. Therefore, detailed explanations of them may be omitted to avoid redundancy.

[0037] Furthermore, even if ordinal numbers such as "first" or "second" are used in the following descriptions, these terms are used for convenience to facilitate understanding of the embodiments and are not limited to the order that may result from these ordinal numbers.

[0038] When expressions indicating relative or absolute positional relationships are used (e.g., "in one direction," "along one direction," "parallel," "orthogonal," "center," "concentric," "coaxial," etc.), unless otherwise specified, such expressions shall not only strictly represent the positional relationship but also represent a state in which there is a relative displacement in terms of angle or distance within a tolerance or a range in which equivalent functionality is obtained. When expressions indicating equality are used (e.g., "identical," "equal," "homogeneous," etc.), unless otherwise specified, such expressions shall not only strictly represent a state in which there is a quantitatively exact equality but also represent a state in which there is a difference within a tolerance or a range in which equivalent functionality is obtained. When expressions indicating shape are used (e.g., "quadrilateral" or "cylindrical"), unless otherwise specified, such expressions shall not only strictly represent the geometrically exact shape but also represent a shape with features such as concavities or chamfers within a range in which equivalent effects are obtained. When expressions such as "possess," "equip," "include," or "have" a single component are used, such expressions are not exclusive expressions that exclude the existence of other components. When the expression "at least one of A, B, and C" is used, it includes A only, B only, C only, any two of A, B, and C, and all of A, B, and C.

[0039] <First Embodiment> <Overall configuration of the substrate processing equipment> Figure 1 is a schematic plan view showing an example of the configuration of the substrate processing apparatus 100. The substrate processing apparatus 100 is a single-wafer processing apparatus that processes substrates W one at a time.

[0040] The substrate W is, for example, a semiconductor wafer, a substrate for liquid crystal displays, an organic electroluminescence (EL) substrate, a flat panel display (FPD) substrate, an optical display substrate, a magnetic disk substrate, an optical disk substrate, a magneto-optical disk substrate, a photomask substrate, or a solar cell substrate. The substrate W has a thin, flat shape. In the following, it is assumed that the substrate W is a semiconductor wafer. The substrate W has, for example, a disc shape. The diameter of the substrate W is, for example, about 300 mm, and the thickness of the substrate W is, for example, about 0.5 mm or more and about 3 mm or less. A pattern is formed on the main surface of the substrate W. The pattern here includes, for example, at least one of a wiring pattern, an electrode pattern, a semiconductor pattern, and an insulating pattern. The aspect ratio of the pattern is, for example, 5 or more and 500 or less. The pattern width is, for example, 3 nm or more and 50 nm or less. Patterns with such high aspect ratios are prone to collapse.

[0041] In the example shown in Figure 1, the substrate processing apparatus 100 includes an indexer block 110, a processing block 120, and a control unit 9. The processing block 120 is primarily responsible for processing the substrate W, while the indexer block 110 is primarily responsible for transporting the substrate W between the outside of the substrate processing apparatus 100 and the processing block 120.

[0042] The indexer block 110 includes a load port 111 and a first transport unit 112. A carrier C brought in from the outside is placed on the load port 111. In other words, the load port 111 includes a platform on which the carrier C is placed. Multiple substrates W are housed in the carrier C. For example, multiple substrates W are housed in the carrier C in a vertical arrangement with spacing between them. In the example in Figure 1, multiple load ports 111 are arranged, and one carrier C is placed on each load port 111.

[0043] The first transport unit 112 is a transport robot capable of removing unprocessed substrates W from carriers C placed on each load port 111. The first transport unit 112 may also be called an indexer robot. The first transport unit 112 transports the unprocessed substrates W removed from the carriers C to the processing block 120. The processing block 120 can process the unprocessed substrates W. The first transport unit 112 can also receive processed substrates W from the processing block 120 and transport the processed substrates W to the carriers C on the load ports 111.

[0044] In the example shown in Figure 1, the processing block 120 includes a plurality of processing units 1 and a second transport unit 122. The second transport unit 122 is a transport robot capable of transporting substrates W between the first transport unit 112 and the plurality of processing units 1. In the example shown in Figure 1, the processing block 120 also includes a mounting unit 123. The mounting unit 123 is provided between the first transport unit 112 and the second transport unit 122. The mounting unit 123 is, for example, a shelf on which a plurality of substrates W can be placed in a vertically aligned position. The first transport unit 112 places the unprocessed substrates W onto the mounting unit 123. The second transport unit 122 removes the unprocessed substrates W from the mounting unit 123 and transports the unprocessed substrates W to the processing unit 1. The processing unit 1 processes the substrates W. The configuration of the processing unit 1 will be described later. The second transport unit 122 removes the processed substrate W from the processing unit 1 and transports the processed substrate W to the mounting unit 123. The first transport unit 112 removes the processed substrate W from the mounting unit 123 and transports the processed substrate W to the carrier C of the load port 111.

[0045] The second transport unit 122 may transport the substrate W between multiple processing units 1 as needed. For example, the second transport unit 122 may transport the substrate W processed in one processing unit 1 to another processing unit 1, and then transport the substrate W processed in that other processing unit 1 to the mounting unit 123.

[0046] In the example shown in Figure 1, multiple processing units 1 are arranged to surround the second transport unit 122 in a plan view. This second transport unit 122 may also be called a center robot. In the example shown in Figure 1, four processing units 1 surround the second transport unit 122. At each position in the plan view where each processing unit 1 is provided, multiple processing units 1 may be stacked vertically. In other words, multiple towers TW (four in the figure) composed of multiple processing units 1 stacked vertically may be arranged to surround the second transport unit 122 in a plan view.

[0047] The control unit 9 can control each component of the substrate processing apparatus 100. The control unit 9 is an electronic circuit device and may have, for example, an arithmetic processing unit and a memory unit. The arithmetic processing unit may be, for example, a CPU (Central Processor Unit). The memory unit may have a non-temporary memory unit (e.g., ROM (Read Only Memory) or hard disk) and a temporary memory unit (e.g., RAM (Random Access Memory)). The non-temporary memory unit may store, for example, a program that defines the processing to be performed by the control unit 9. By executing this program, the processing apparatus can enable the control unit 9 to perform the processing defined in the program. Of course, some or all of the processing performed by the control unit 9 may be performed by hardware.

[0048] <Overview of the processing unit> Figure 2 is a schematic longitudinal cross-sectional view showing an example of the configuration of a processing unit 1 according to the first embodiment. Note that not all processing units 1 belonging to the substrate processing apparatus 100 need to have the configuration exemplified in Figure 2. It is sufficient that at least one processing unit 1 of the substrate processing apparatus 100 has the configuration exemplified in Figure 2.

[0049] The processing unit 1 can perform a hydrophobic treatment to make the main surface of the substrate W hydrophobic. In the example shown in Figure 2, the processing unit 1 includes a chamber 10, a substrate holding section 2, at least one central nozzle 3, a first hydrophobic pipe 31h, a first hydrophobic adjustment valve 32h, at least one peripheral nozzle 4, a second hydrophobic pipe 41h, and a second hydrophobic adjustment valve 42h.

[0050] Chamber 10 has a box-like shape, and its internal space corresponds to a processing space for processing substrates W. Chamber 10 is provided with an openable and closable discharge / exit port (not shown). The second transport unit 122 transports unprocessed substrates W into Chamber 10 through the discharge / exit port and discharges processed substrates W from Chamber 10 through the discharge / exit port.

[0051] The substrate holder 2 is located inside the chamber 10 and rotates the substrate W around the rotation axis Q1 while holding it in a horizontal position. Here, "horizontal position" refers to a position where the thickness direction of the substrate W is aligned with the vertical direction. The rotation axis Q1 is an axis that passes through the center of the substrate W and is aligned with the vertical direction. Such a substrate holder 2 may also be called a spin chuck. In this case, the main surface of the substrate W on which the pattern is formed faces vertically upward. That is, the pattern is formed on the upper surface of the substrate W held by the substrate holder 2.

[0052] At least one central nozzle 3 is provided within the chamber 10 and discharges fluid toward the center of the main surface of the substrate W held by the substrate holding section 2. In the example in Figure 2, one of the central nozzles 3 is shown as central nozzle 3h. The central nozzle 3h discharges hydrophobic liquid as a fluid toward the center of the main surface of the substrate W held by the substrate holding section 2. The central nozzle 3h is, for example, a straight nozzle that discharges the hydrophobic liquid in a continuous flow state. In the example in Figure 2, the central nozzle 3h discharges the hydrophobic liquid toward the upper surface of the substrate W. That is, in the example in Figure 2, the central nozzle 3h is located above the substrate W held by the substrate holding section 2. The hydrophobic liquid discharged from the central nozzle 3h lands on the center of the main surface of the substrate W.

[0053] A hydrophobic solution is a liquid that imparts hydrophobicity to a substrate W. Hydrophobic solutions include, for example, silicon-based hydrophobic solutions. Silicon-based hydrophobic solutions are hydrophobic solutions that hydrophobicize silicon (Si) itself and silicon-containing compounds. A hydrophobic solution is, for example, a silylation solution containing a liquid silylation agent (also called a silane coupling agent). This silylation agent is an organosilicon compound having an ethoxy (or methoxy) group at one end of the molecule that gives a silanol group (Si-OH) upon hydrolysis, and an organic functional group such as an amino group or a glycidyl group at the other end. Silylation agents include, for example, HMDS (hexamethyldisilazane), TMS (tetramethylsilane), fluorinated alkylchlorosilane, alkyldisilazane, and at least one of non-chloro-based hydrophobic solutions. The non-chlorohydrophobic solution includes, for example, dimethylsilyldimethylamine, dimethylsilyldiethylamine, hexamethyldisilazane, tetramethyldisilazane, bis(dimethylamino)dimethylsilane, N,N-dimethylaminotrimethylsilane, N-(trimethylsilyl)dimethylamine, and at least one organosilane compound.

[0054] The downstream end of the first hydrophobic pipe 31h is connected to the central nozzle 3h. The upstream end of the first hydrophobic pipe 31h is connected to a hydrophobic liquid supply source (not shown). The hydrophobic liquid supply source includes a tank (not shown) for storing the hydrophobic liquid.

[0055] The first hydrophobic control valve 32h is inserted into the first hydrophobic pipe 31h. The first hydrophobic control valve 32h adjusts the flow rate of the hydrophobic liquid flowing through the first hydrophobic pipe 31h, that is, the flow rate of the hydrophobic liquid discharged from the central nozzle 3h. The first hydrophobic control valve 32h is, for example, a mass flow controller. A mass flow controller can also be applied to other specific examples of flow control valves described later. Hereafter, the flow rate of the hydrophobic liquid flowing through the first hydrophobic pipe 31h, that is, the flow rate of the hydrophobic liquid discharged from the central nozzle 3h, will be referred to as the first hydrophobic flow rate Fh1.

[0056] At least one peripheral nozzle 4 is provided within the chamber 10 and discharges fluid toward the peripheral edge of the main surface of the substrate W held by the substrate holder 2. In the example in Figure 2, peripheral nozzle 4h is shown as one of the peripheral nozzles 4. Peripheral nozzle 4h discharges hydrophobic liquid as a fluid toward the peripheral edge of the main surface of the substrate W held by the substrate holder 2. Peripheral nozzle 4h is, for example, a straight nozzle that discharges the hydrophobic liquid in a continuous flow state. As an example, peripheral nozzle 4h discharges the hydrophobic liquid toward the upper surface of the substrate W. That is, peripheral nozzle 4h is located above the substrate W held by the substrate holder 2. As shown in Figure 2, peripheral nozzle 4h may be provided radially outward from the substrate W in a plan view. Peripheral nozzle 4h may be fixed immovably to the chamber 10. That is, peripheral nozzle 4h may be a fixed nozzle. Peripheral nozzle 4h discharges the hydrophobic liquid, for example, along an oblique downward direction. The hydrophobic liquid discharged from the peripheral nozzle 4h adheres to the peripheral area of ​​the main surface of the substrate W.

[0057] The point of contact of the hydrophobic liquid discharged from the peripheral nozzle 4h onto the main surface of the substrate W may, for example, be within a virtual annular region described below. The virtual center of the annular region coincides with the axis of rotation Q1. The virtual outer diameter of the annular region may be, for example, 90%, 80%, or 70% of the diameter of the substrate W. The virtual inner diameter of the annular region may be, for example, 10%, 20%, 30%, or 40% of the diameter of the substrate W.

[0058] The downstream end of the second hydrophobic pipe 41h is connected to the peripheral nozzle 4h. The upstream end of the second hydrophobic pipe 41h is connected to a hydrophobic liquid supply source (not shown).

[0059] The second hydrophobic control valve 42h is inserted into the second hydrophobic pipe 41h. The second hydrophobic control valve 42h adjusts the flow rate of the hydrophobic liquid flowing through the second hydrophobic pipe 41h, that is, the flow rate of the hydrophobic liquid discharged from the peripheral nozzle 4h. Hereinafter, the flow rate of the hydrophobic liquid flowing through the second hydrophobic pipe 41h, that is, the flow rate of the hydrophobic liquid discharged from the peripheral nozzle 4h, will be referred to as the second hydrophobic flow rate Fh2.

[0060] The first hydrophobic control valve 32h and the second hydrophobic control valve 42h are controlled by the control unit 9. In other words, the control unit 9 controls the first hydrophobic control valve 32h and the second hydrophobic control valve 42h to discharge the hydrophobized liquid from the central nozzle 3h and the peripheral nozzle 4h at the first hydrophobic flow rate Fh1 and the second hydrophobic flow rate Fh2, respectively.

[0061] Furthermore, a heater for heating the hydrophobic solution may be provided in at least one of the first hydrophobic pipe 31h and the second hydrophobic pipe 41h. The heater may be, for example, an electrically resistive heater having a heating wire, or an optical heater that irradiates heating light. The heater may raise the temperature of the hydrophobic solution to a temperature suitable for the hydrophobic treatment.

[0062] In the example shown in Figure 2, a first hydrophobic valve 33h is interposed in the first hydrophobic pipe 31h, and a second hydrophobic valve 43h is interposed in the second hydrophobic pipe 41h. The first hydrophobic valve 33h switches the flow path of the first hydrophobic pipe 31h open and closed. The second hydrophobic valve 43h switches the flow path of the second hydrophobic pipe 41h open and closed. The first hydrophobic valve 33h and the second hydrophobic valve 43h are controlled by the control unit 9.

[0063] When at least one of the first hydrophobic valve 33h and the second hydrophobic valve 43h opens, the hydrophobic solution is supplied to the main surface of the substrate W. Hereinafter, the treatment period during which the hydrophobic solution is supplied to the substrate W will also be referred to as the hydrophobic treatment period.

[0064] During the hydrophobic treatment period, the control unit 9 controls the first hydrophobic control valve 32h and the second hydrophobic control valve 42h to adjust the ratio of the first hydrophobic flow rate Fh1 to the second hydrophobic flow rate Fh2 (=Fh1 / Fh2). Hereinafter, this ratio will be referred to as the hydrophobic flow rate ratio. As will be described in detail later, the control unit 9 controls the first hydrophobic control valve 32h and the second hydrophobic control valve 42h to make the hydrophobic flow rate ratio in the first period, which is part of the hydrophobic treatment period, higher than the hydrophobic flow rate ratio in the second period, which is later than the first period of the hydrophobic treatment period. The technical significance of this will be described in detail later.

[0065] <An example of a specific configuration of a processing unit> Referring to Figure 2, a more specific example of the configuration of the processing unit 1 will be described. In the example in Figure 2, a fan filter unit 11 is installed on the ceiling of the chamber 10. The fan filter unit 11 is a device that takes in air from outside the chamber 10, purifies it, and blows the purified air into the chamber 10. The fan filter unit 11 is controlled by the control unit 9. The operation of the fan filter unit 11 creates a downflow of clean air inside the chamber 10.

[0066] In the example shown in Figure 2, the processing unit 1 is provided with an exhaust duct 13. In the example shown in Figure 2, the exhaust duct 13 is connected to the lower part of the side wall of the chamber 10. The gas inside the chamber 10 is discharged to the outside through the exhaust duct 13.

[0067] In the example shown in Figure 2, the substrate holder 2 includes a spin base 21, a plurality of chuck pins 22, and a rotation mechanism 23. The spin base 21 has a disc shape and is positioned so that its thickness direction is aligned with the vertical direction. The spin base 21 is positioned so that its center coincides with the rotation axis Q1. The plurality of chuck pins 22 are erected on the periphery of the spin base 21 at equal intervals along the circumferential direction with respect to the rotation axis Q1. Each chuck pin 22 is provided to be movable between a contact position and a separated position, which will be described below. The contact position is the position where the chuck pin 22 contacts the periphery of the substrate W. When each chuck pin 22 is in the contact position, the plurality of chuck pins 22 can hold the substrate W. The separated position is the position where the chuck pin 22 is separated from the substrate W. When each chuck pin 22 is in the separated position, the holding of the substrate W by the plurality of chuck pins 22 is released. The substrate holding section 2 does not necessarily need to include the chuck pins 22; for example, the substrate W may be held by a Bernoulli chuck, a suction chuck, or an electrostatic chuck.

[0068] The rotation mechanism 23 rotates the substrate W around the rotation axis Q1. In the example in Figure 2, the rotation mechanism 23 includes a shaft 231 and a motor 232. The upper end of the shaft 231 is connected to the lower surface of the spin base 21 and extends along the rotation axis Q1. The motor 232 rotates the shaft 231 around the rotation axis Q1. As a result, the spin base 21, which is fixed to the shaft 231, rotates around the rotation axis Q1, and the substrate W, which is held by a plurality of chuck pins 22, also rotates around the rotation axis Q1.

[0069] In the example shown in Figure 2, the processing unit 1 also includes a chemical nozzle 6 located within the chamber 10. The chemical nozzle 6 discharges the chemical solution toward the main surface (in this case, the top surface) of the substrate W held by the substrate holding unit 2. The chemical nozzle 6 is, for example, a straight nozzle that discharges the chemical solution in a continuous flow state. The chemical solution may be an acidic or alkaline solution. As a specific example, dilute hydrofluoric acid, a mixture of hydrofluoric acid and hydrogen peroxide, or phosphoric acid can be used as the chemical solution.

[0070] The downstream end of the chemical solution pipe 61 is connected to the chemical solution nozzle 6. The upstream end of the chemical solution pipe 61 is connected to a chemical solution supply source (not shown). The chemical solution supply source includes a tank (not shown) for storing the chemical solution. A chemical solution adjustment valve 62 and a chemical solution on / off valve 63 are interposed in the chemical solution pipe 61. The chemical solution adjustment valve 62 adjusts the flow rate of the chemical solution flowing through the chemical solution pipe 61. The chemical solution on / off valve 63 switches the flow path of the chemical solution pipe 61 open and closed. The chemical solution adjustment valve 62 and the chemical solution on / off valve 63 are controlled by the control unit 9.

[0071] In the example shown in Figure 2, the processing unit 1 is provided with a nozzle moving mechanism 65 for moving the chemical nozzle 6. The nozzle moving mechanism 65 moves the chemical nozzle 6 between the chemical processing position and the chemical standby position, which will be described below. The chemical processing position is the position where the chemical nozzle 6 discharges the chemical solution toward the substrate W held by the substrate holding unit 2, for example, a position perpendicular to the center of the main surface of the substrate W. The chemical standby position is the position where the chemical nozzle 6 does not discharge the chemical solution toward the substrate W, for example, a position radially outside the substrate W. In the example shown in Figure 2, the chemical nozzle 6 stopped at the chemical standby position is shown. For example, the nozzle moving mechanism 65 includes a motor as a drive source. An example of a specific configuration of the nozzle moving mechanism 65 is the same as an example of a specific configuration of the nozzle moving mechanism 35 described later.

[0072] When the chemical solution discharged from the chemical solution nozzle 6, which has stopped at the chemical solution application position, lands on the center of the main surface of the rotating substrate W, the chemical solution spreads on the main surface of the substrate W and scatters outward from the periphery of the substrate W. At this time, the chemical solution acts on the main surface of the substrate W. As a result, a treatment corresponding to the chemical solution is performed on the substrate W. For example, a treatment (cleaning treatment) is performed to remove foreign matter adhering to the main surface of the substrate W.

[0073] In the example shown in Figure 2, the processing unit 1 also includes a central nozzle 3r and a central nozzle 3i, which serve as the central nozzle 3. The central nozzle 3r discharges the rinsing liquid toward the center of the main surface of the substrate W held by the substrate holding unit 2. The central nozzle 3r is, for example, a straight nozzle that discharges the rinsing liquid in a continuous flow state. In the example shown in Figure 2, the central nozzle 3r discharges the rinsing liquid toward the upper surface of the substrate W. That is, the central nozzle 3r is located above the substrate W held by the substrate holding unit 2. The rinsing liquid discharged from the central nozzle 3r lands on the center of the main surface of the substrate W. The rinsing liquid is, for example, one of the following: pure water, carbonated water, electrolyzed ionized water, hydrogen water, ozonated water, and hydrochloric acid water (hydrochloric acid water with a dilution concentration of about 10 to 100 ppm).

[0074] The downstream end of the first rinse pipe 31r is connected to the central nozzle 3r. The upstream end of the first rinse pipe 31r is connected to a rinse liquid supply source (not shown). The rinse liquid supply source includes a tank (not shown) for storing the rinse liquid. The first rinse pipe 31r has a first rinse control valve 32r and a first rinse on / off valve 33r inserted between them. The first rinse control valve 32r adjusts the flow rate of the rinse liquid flowing through the first rinse pipe 31r. The first rinse on / off valve 33r switches the flow path of the first rinse pipe 31r open and closed. The first rinse control valve 32r and the first rinse on / off valve 33r are controlled by the control unit 9.

[0075] When the rinsing liquid discharged from the central nozzle 3r lands on the center of the main surface of the rotating substrate W, the rinsing liquid spreads across the main surface of the substrate W and splashes outwards from the periphery of the substrate W. The rinsing liquid can push the chemical solution on the main surface of the substrate W outwards (rinsing process). This allows the chemical solution on the main surface of the substrate W to be replaced by the rinsing liquid.

[0076] The central nozzle 3i discharges the organic solvent toward the center of the main surface of the substrate W held by the substrate holding section 2. The central nozzle 3i is, for example, a straight nozzle that discharges the organic solvent in a continuous flow. In the example shown in Figure 2, the central nozzle 3i discharges the organic solvent toward the upper surface of the substrate W. In other words, the central nozzle 3i is located above the substrate W held by the substrate holding section 2. The organic solvent discharged from the central nozzle 3i lands on the center of the main surface of the substrate W.

[0077] An example of an organic solvent is isopropyl alcohol. The volatility of the organic solvent is higher than that of the rinsing solution. Alcohols such as methyl alcohol, ethanol, and propyl alcohol can also be used as organic solvents. Other organic solvents that can be used include ketones, PGMEA (propylene glycol monomethyl ether acetate), EGMEA (ethylene glycol monomethyl ether), and at least one of fluorinated solvents.

[0078] The downstream end of the first solvent pipe 31i is connected to the central nozzle 3i. The upstream end of the first solvent pipe 31i is connected to an organic solvent supply source (not shown). The organic solvent supply source includes a tank (not shown) for storing the organic solvent. A first solvent control valve 32i and a first solvent on / off valve 33i are interposed in the first solvent pipe 31i. The first solvent control valve 32i adjusts the flow rate of the organic solvent flowing through the first solvent pipe 31i. The first solvent on / off valve 33i switches the flow path of the first solvent pipe 31i open and closed. The first solvent control valve 32i and the first solvent on / off valve 33i are controlled by the control unit 9.

[0079] When the organic solvent discharged from the central nozzle 3i lands on the center of the main surface of the rotating substrate W, the organic solvent spreads across the main surface of the substrate W and scatters outward from the periphery of the substrate W. The organic solvent can push away any liquid on the main surface of the substrate W (e.g., rinse solution or hydrophobic solution) (solvent treatment). This allows the liquid on the main surface of the substrate W to be replaced with the organic solvent.

[0080] In the example shown in Figure 2, the processing unit 1 also includes a central nozzle 3g as a central nozzle 3. The central nozzle 3g discharges an inert gas toward the center of the main surface of the substrate W held by the substrate holder 2. In the example shown in Figure 2, the central nozzle 3g discharges an inert gas toward the upper surface of the substrate W. In other words, the central nozzle 3g is located above the substrate W held by the substrate holder 2. The inert gas includes, for example, nitrogen gas and at least one of a noble gas. The noble gas includes, for example, argon gas.

[0081] In the example shown in Figure 2, the central nozzles 3h, 3r, 3i, and 3g are integrated. In the example shown in Figure 2, the central nozzles 3h, 3r, and 3i are located within the internal flow path of the central nozzle 3g. The central nozzles 3h, 3r, and 3i are positioned adjacent to each other horizontally and are fixed, for example, to the upper end of the central nozzle 3g. The internal flow path of the central nozzle 3g opens downwards. Therefore, the hydrophobic liquid discharged from the central nozzle 3h flows down from the lower opening of the central nozzle 3g toward the upper surface of the substrate W. Similarly, the rinsing liquid from the central nozzle 3r and the organic solvent from the central nozzle 3i also flow down from the lower opening of the central nozzle 3g toward the upper surface of the substrate W.

[0082] The internal flow path of the central nozzle 3g is connected to the downstream end of the first gas pipe 31g. The upstream end of the first gas pipe 31g is connected to a gas supply source (not shown). The gas supply source includes a storage section (not shown) for storing inert gas. A first gas regulating valve 32g and a first gas on / off valve 33g are interposed in the first gas pipe 31g. The first gas regulating valve 32g adjusts the flow rate of inert gas flowing through the first gas pipe 31g. The first gas on / off valve 33g switches the flow path of the first gas pipe 31g open and closed. The first gas regulating valve 32g and the first gas on / off valve 33g are controlled by the control unit 9.

[0083] When the inert gas discharged from the central nozzle 3g collides with the center of the main surface of the rotating substrate W, the inert gas flows radially outward along the main surface of the substrate W. By supplying the inert gas to the main surface of the substrate W in this way, the drying of the main surface of the substrate W can be promoted.

[0084] In the example shown in Figure 2, the processing unit 1 is provided with a nozzle moving mechanism 35 for moving the central nozzle 3. Here, the nozzle moving mechanism 35 moves the central nozzles 3h, 3r, 3i, and 3g together. Hereafter, the configuration consisting of the central nozzles 3h, 3i, 3r, and 3g will also be referred to as the central nozzle head. The nozzle moving mechanism 35 moves the central nozzle head between the central processing position and the head standby position, which will be described next. The central processing position is the position where at least one of the central nozzles 3 discharges fluid toward the center of the main surface of the substrate W held by the substrate holding unit 2, for example, a position perpendicular to the center of the substrate W. The head standby position is the position where each central nozzle 3 does not discharge fluid toward the main surface of the substrate W, for example, a position radially outside the substrate W.

[0085] In the example shown in Figure 2, the nozzle moving mechanism 35 includes an arm 351, a support column 352, and a drive source 353. The support column 352 is located radially outward from the guard portion 7 (described later) and extends vertically. The arm 351 extends horizontally, its tip connected to the central nozzle head, and its base connected to the support column 352. The drive source 353 rotates the support column 352 around its central axis Q2. The drive source 353 includes, for example, a motor. As the support column 352 rotates around the central axis Q2, the central nozzle head moves along the circumferential direction with respect to the central axis Q2. The support column 352 is installed such that the central processing position and the head standby position are located on the movement trajectory of the central nozzle head. Note that the nozzle moving mechanism 35 is not necessarily limited to the embodiment shown in Figure 2, and may include, for example, a linear motion mechanism such as a linear motor.

[0086] In the example shown in Figure 2, the processing unit 1 is provided with a guard section 7 that catches various processing liquids scattered from the periphery of the substrate W. The processing liquids referred to here are a general term for chemical solutions, rinsing solutions, and organic solvents. The guard section 7 includes at least one guard 71. The guard 71 has a cylindrical (for example, cylindrical) shape that surrounds the substrate W held by the substrate holding section 2. In the example shown in Figure 2, the guard section 7 includes a plurality of guards 71 ​​(three in the figure) arranged concentrically.

[0087] Each of the multiple guards 71 ​​moves up and down between a guard processing position and a guard standby position, as described below, by a guard lifting mechanism 73. The guard processing position is the position where the upper end of the guard 71 is vertically above the upper surface of the substrate W held by the substrate holding part 2. When the guard 71 is stopped at the guard processing position, the processing liquid scattered from the periphery of the substrate W is received by the inner surface of the guard 71. The guard standby position is a position lower than the guard processing position, for example, where the upper end of the guard 71 is below the upper surface of the spin base 21. The guard lifting mechanism 73 may include, for example, a motor as a drive source and a ball screw mechanism as a drive mechanism. Alternatively, the guard lifting mechanism 73 may include an air cylinder.

[0088] In the example shown in Figure 2, the guard section 7 includes a drain tank 72 corresponding to each guard 71. Each drain tank 72 receives the treated liquid that flows down along the inner circumferential surface of the corresponding guard 71. The upstream end of the drain pipe 12 is connected to the bottom of each drain tank 72. The treated liquid is recovered from the drain tank 72 through the drain pipe 12.

[0089] The processing unit 1 may be provided with a heater (not shown) for heating the substrate W held by the substrate holding unit 2. For example, the heater may be provided between the spin base 21 and the substrate W. The heater may be, for example, an electrically resistive heater having a heating wire, or an optical heater that irradiates heating electromagnetic waves. Alternatively, the heater may heat the substrate W by supplying a high-temperature fluid to, for example, the underside of the substrate W. The heater may heat the substrate W to a temperature suitable for each processing liquid.

[0090] <An example of the operation of a substrate processing device> Next, an example of the operation of the processing unit 1 will be described. Figure 3 is a flowchart showing an example of the operation of the processing unit 1. First, the second transport unit 122 transports the substrate W to the processing unit 1, and the substrate holding unit 2 holds the substrate W received from the second transport unit 122 (Step S1: Holding step).

[0091] Next, the substrate holder 2 starts rotating the substrate W (step S2: rotation process). As a result, the substrate W rotates around the rotation axis Q1. The substrate holder 2 may continue rotating the substrate W until a series of processes on the substrate W is completed.

[0092] Next, the processing unit 1 performs chemical treatment (Step S3: Chemical Treatment Process). Specifically, first, the guard lifting mechanism 73 moves the guard 71 corresponding to the chemical treatment to the guard treatment position, and the nozzle moving mechanism 65 moves the chemical treatment nozzle 6 to the chemical treatment position. Then, the chemical treatment valve 63 opens. As a result, the chemical treatment nozzle 6 discharges the chemical treatment toward the main surface of the rotating substrate W. The chemical treatment lands on the center of the main surface of the substrate W, spreads out on the main surface of the substrate W, and splashes from the periphery of the substrate W. The chemical treatment is received by the inner surface of the guard 71 corresponding to the chemical treatment. At this time, the chemical treatment acts on the main surface of the substrate W, and treatment corresponding to the chemical treatment is performed on the main surface of the substrate W. When a predetermined chemical treatment time has elapsed from the start of chemical treatment supply, the chemical treatment valve 63 closes. The time can be measured, for example, by a timer circuit (not shown) belonging to the control unit 9. When the chemical treatment valve 63 closes, the chemical treatment is substantially completed. Then, the nozzle moving mechanism 65 moves the chemical solution nozzle 6 to the chemical solution standby position.

[0093] Next, the processing unit 1 performs a rinsing process (Step S4: Rinsing process). Specifically, first, the nozzle moving mechanism 35 moves the central nozzle head to the central processing position. If the guard 71 corresponding to the rinsing liquid is different from the guard 71 corresponding to the chemical solution, the guard lifting mechanism 73 moves the guard 71 corresponding to the rinsing liquid to the guard processing position. Then, the first rinsing on / off valve 33r opens. As a result, the central nozzle 3r discharges the rinsing liquid toward the center of the main surface of the substrate W. The flow rate of the rinsing liquid is set, for example, to be between approximately 1500 ccm and 2000 ccm. The rinsing liquid lands on the center of the main surface of the substrate W, spreads on the main surface of the substrate W, and splashes outwards from the periphery of the substrate W. The rinsing liquid is received by the inner surface of the guard 71 corresponding to the rinsing liquid. The rinsing solution applied to the center of the main surface of the substrate W pushes the chemical solution on the main surface of the substrate W radially outward, thereby replacing the chemical solution on the main surface of the substrate W with the rinsing solution. After a predetermined rinsing time has elapsed from the start of rinsing solution supply, the first rinsing valve 33r closes. This effectively completes the rinsing process.

[0094] Next, the processing unit 1 performs a pre-solvent treatment (Step S5: Pre-solvent process). Specifically, if the guard 71 corresponding to the organic solvent is different from the guard 71 corresponding to the rinse liquid, the guard lifting mechanism 73 moves the guard 71 corresponding to the organic solvent to the guard treatment position. Then, the first solvent on / off valve 33i opens. As a result, the central nozzle 3i discharges the organic solvent toward the center of the main surface of the rotating substrate W. The flow rate of the organic solvent is smaller than the flow rate of the rinse liquid, for example, set to half or one-third of the flow rate of the rinse liquid. As a more specific example, the flow rate of the organic solvent is set to be greater than 200 ccm and 400 ccm or less, for example, set to about 300 ccm. The organic solvent lands on the center of the main surface of the substrate W, spreads on the main surface of the substrate W, and scatters outwards from the periphery of the substrate W. The organic solvent is received by the inner surface of the guard 71 corresponding to the organic solvent. The organic solvent applied to the center of the main surface of the substrate W pushes the rinse liquid on the main surface of the substrate W radially outward, thereby replacing the rinse liquid on the main surface of the substrate W with the organic solvent. After a predetermined pre-treatment time has elapsed since the start of supplying the organic solvent, the first solvent on / off valve 33i closes. This effectively completes the pre-solvent treatment.

[0095] Next, the processing unit 1 performs a hydrophobic treatment (Step S6: Hydrophobic treatment). Specifically, if the guard 71 corresponding to the hydrophobic liquid is different from the guard 71 corresponding to the organic solvent, the guard lifting mechanism 73 moves the guard 71 corresponding to the hydrophobic liquid to the guard treatment position. Then, the first hydrophobic valve 33h and the second hydrophobic valve 43h open. As a result, the central nozzle 3h and the peripheral nozzle 4h discharge the hydrophobic liquid toward the main surface of the rotating substrate W. The hydrophobic liquid discharged from the central nozzle 3h lands on the central part of the main surface of the substrate W, spreads on the main surface of the substrate W, and scatters outward from the periphery of the substrate W. The hydrophobic liquid discharged from the peripheral nozzle 4h lands on the peripheral part of the main surface of the substrate W, flows radially outward on the main surface of the substrate W, and scatters outward from the periphery of the substrate W. The hydrophobic liquid is received by the inner circumferential surface of the guard 71 corresponding to the hydrophobic liquid.

[0096] The hydrophobic solution can wash away the organic solvent on the main surface of the substrate W, thereby replacing the organic solvent on the main surface of the substrate W with the hydrophobic solution. At the same time, the hydrophobic solution acts on the main surface of the substrate W, forming a hydrophobic film on the main surface of the substrate W. In other words, the main surface of the substrate W becomes hydrophobic.

[0097] During the hydrophobic treatment period Th in which the hydrophobic solution is supplied to the substrate W, the control unit 9 controls the first hydrophobic adjustment valve 32h and the second hydrophobic adjustment valve 42h to change the hydrophobic flow rate ratio (=Fh1 / Fh2) between the first hydrophobic flow rate Fh1 and the second hydrophobic flow rate Fh2. The sum of the first hydrophobic flow rate Fh1 and the second hydrophobic flow rate Fh2 is set to be smaller than, for example, the flow rate of the rinse solution and also smaller than the flow rate of the organic solvent. The sum of the first hydrophobic flow rate Fh1 and the second hydrophobic flow rate Fh2 is set to be less than or equal to one-fifth or one-tenth of the flow rate of the rinse solution. As a more specific example, the sum of the first hydrophobic flow rate Fh1 and the second hydrophobic flow rate Fh2 is set to be between approximately 50 ccm and approximately 200 ccm, for example, set to approximately 150 ccm.

[0098] Figure 4 is a schematic diagram showing an example of the state of the treatment unit 1 during hydrophobic treatment, and Figure 5 is a graph showing the first example of the time change of the first hydrophobic flow rate Fh1 and the second hydrophobic flow rate Fh2. In the example of Figure 5, the hydrophobic treatment period Th consists of periods Th1, Th2, and Th3. Here, period Th2 is the period following period Th1, and period Th3 is the period following period Th2. Figure 4(a) shows an example of the state of the treatment unit 1 during period Th1, Figure 4(b) shows an example of the state of the treatment unit 1 during period Th2, and Figure 4(c) shows an example of the state of the treatment unit 1 during period Th3. In the examples of Figures 4(a) to 4(c), the magnitude of the first hydrophobic flow rate Fh1 of the hydrophobic liquid discharged from the central nozzle 3h and the second hydrophobic flow rate Fh2 of the hydrophobic liquid discharged from the peripheral nozzle 4h are schematically shown by the width of the liquid column of the hydrophobic liquid.

[0099] As shown in Figures 4 and 5, the control unit 9 makes the hydrophobic flow rate ratio (=Fh1 / Fh2) in period Th1 higher than the hydrophobic flow rate ratio in period Th2, and makes the hydrophobic flow rate ratio in period Th2 higher than the hydrophobic flow rate ratio in period Th3. In other words, the control unit 9 controls the first hydrophobic control valve 32h and the second hydrophobic control valve 42h so that the hydrophobic flow rate ratio decreases over time. The hydrophobic flow rate ratio in period Th1 may be, for example, 1.5 or more. The second hydrophobic flow rate Fh2 in period Th1 may be zero. The hydrophobic flow rate ratio in period Th2 may be, for example, 0.8 or more and less than 1.5. The hydrophobic flow rate ratio in period Th3 may be, for example, 0.01 or more and less than 0.8.

[0100] The lengths (i.e., time) of periods Th1, Th2, and Th3 may be set in advance and stored in the memory unit of the control unit 9.

[0101] In the example shown in Figure 5, the control unit 9 controls the first hydrophobic control valve 32h so that the first hydrophobic flow rate Fh1 in period Th1 is greater than the first hydrophobic flow rate Fh1 in period Th2, and the first hydrophobic flow rate Fh1 in period Th2 is greater than the first hydrophobic flow rate Fh1 in period Th3. In other words, in the example shown in Figure 5, the control unit 9 controls the first hydrophobic control valve 32h so that the first hydrophobic flow rate Fh1 decreases over time.

[0102] Furthermore, in the example shown in Figure 5, the control unit 9 controls the second hydrophobic control valve 42h so that the second hydrophobic flow rate Fh2 in period Th1 is smaller than the second hydrophobic flow rate Fh2 in period Th2, and the second hydrophobic flow rate Fh2 in period Th2 is smaller than the second hydrophobic flow rate Fh2 in period Th3. In other words, in the example shown in Figure 5, the control unit 9 controls the second hydrophobic control valve 42h so that the second hydrophobic flow rate Fh2 increases over time.

[0103] In the example shown in Figure 5, the control unit 9 controls the first hydrophobic control valve 32h and the second hydrophobic control valve 42h so that the first hydrophobic flow rate Fh1 in period Th1 is greater than the second hydrophobic flow rate Fh2 in period Th1, the first hydrophobic flow rates Fh1 and Fh2 are equal to each other in period Th2, and the first hydrophobic flow rate Fh1 in period Th3 is less than the second hydrophobic flow rate Fh2 in period Th3. In other words, in the example shown in Figure 5, the control unit 9 controls the first hydrophobic control valve 32h and the second hydrophobic control valve 42h so that the relative magnitudes of the first hydrophobic flow rate Fh1 and the second hydrophobic flow rate Fh2 are reversed over time.

[0104] As described above, during the first period of the hydrophobic treatment (for example, period Th1), the hydrophobic flow rate ratio is relatively high. Therefore, a large amount of hydrophobic solution adheres to the central part of the substrate W, and a small amount adheres to the peripheral part of the substrate W. Consequently, a large amount of hydrophobic solution can push the organic solvent on the main surface of the substrate W from the center outwards. Therefore, the organic solvent on the central part of the main surface of the substrate W can be replaced with the hydrophobic solution more quickly.

[0105] Furthermore, the larger volume of hydrophobic solution deposited in the center pushes the organic solvent outward from the center of the substrate W, acting on the main surface of the substrate W and hydrophobicizing it. This reaction consumes the components required for hydrophobicizing the substrate W, and these components also react with the moisture in the internal space of the chamber 10. As a result, the activity of the hydrophobic solution decreases as you move from the center of the substrate W towards the periphery. In other words, the hydrophobic solution deposited in the center becomes inactive as you move towards the periphery of the substrate W.

[0106] In this embodiment, the hydrophobic solution from the peripheral nozzle 4 is deposited on the peripheral portion of the substrate W. Therefore, a nearly inactive hydrophobic solution can act on the peripheral portion of the substrate W, contributing to the hydrophobicization of the peripheral portion of the substrate W. However, in the first period (for example, period Th1), a relatively small amount of hydrophobic solution is deposited on the peripheral portion, so hydrophobicization mainly progresses in the central portion of the substrate W.

[0107] The hydrophobic flow rate ratio in the second period (e.g., period Th2 or period Th3) is lower than the hydrophobic flow rate ratio in the first period (e.g., period Th1). In the example in Figure 5, in period Th2, the first hydrophobic flow rate Fh1 and the second hydrophobic flow rate Fh2 are equal. Therefore, in period Th2, the hydrophobic solution is deposited on the central and peripheral parts of the substrate W at roughly the same flow rate. Consequently, hydrophobicization of the central and peripheral parts of the substrate W progresses to roughly the same extent.

[0108] In the example shown in Figure 5, the hydrophobic flow rate ratio during period Th3 is lower than that during period Th2. Therefore, during period Th3, a smaller amount of hydrophobic solution adheres to the central part of the substrate W, while a larger amount adheres to the peripheral parts of the substrate W. Consequently, during period Th3, hydrophobicization primarily progresses to the peripheral parts of the substrate W. Therefore, the peripheral parts of the substrate W can also be properly hydrophobicized. Furthermore, since the hydrophobic solution adheres to the central part of the substrate W even during period Th3, the hydrophobic solution can cover the entire main surface of the substrate W. Therefore, the possibility of impurities adhering to the main surface of the substrate W can be reduced.

[0109] Once period Th3 has elapsed, the first hydrophobic valve 33h and the second hydrophobic valve 43h close. This effectively completes the hydrophobic treatment.

[0110] Next, the processing unit 1 performs a post-solvent treatment (step S7: post-solvent process). Specifically, if the guard 71 corresponding to the hydrophobic liquid is different from the guard 71 corresponding to the organic solvent, the guard lifting mechanism 73 moves the guard 71 corresponding to the organic solvent to the guard treatment position. Then, the first solvent on / off valve 33i opens. As a result, the central nozzle 3i discharges the organic solvent toward the center of the main surface of the rotating substrate W. The flow rate of the organic solvent is set, for example, within the same range as described in the pre-solvent process. The organic solvent lands on the center of the main surface of the substrate W, spreads on the main surface of the substrate W, and splashes outwards from the periphery of the substrate W. The organic solvent is received by the inner surface of the guard 71 corresponding to the organic solvent. The organic solvent that lands on the center of the substrate W pushes away the hydrophobic liquid on the main surface of the substrate W, so that the hydrophobic liquid on the main surface of the substrate W can be replaced with the organic solvent. After a predetermined post-treatment time has elapsed from the start of organic solvent supply, the first solvent on / off valve 33i closes. This effectively completes the post-solvent treatment.

[0111] Next, the processing unit 1 performs a drying process (Step S8: Drying process). Specifically, the substrate holding unit 2 increases the rotation speed of the substrate W. This increases the amount of organic solvent scattered from the periphery of the substrate W. It also promotes the vaporization of the organic solvent on the main surface of the substrate W. During this drying process, the first gas on / off valve 33g may be opened. In this case, the central nozzle 3g discharges inert gas toward the center of the main surface of the rotating substrate W. The inert gas collides with the center of the substrate W and flows outward along the main surface of the substrate W. This promotes the vaporization of the organic solvent on the main surface of the substrate W. In addition, since the inert gas presses the organic solvent on the main surface of the substrate W radially outward, it also increases the amount of organic solvent scattered from the periphery of the substrate W.

[0112] If the main surface of the substrate W is hydrophobic, the contact angle of the liquid surface of the organic solvent between patterns can be brought closer to 90 degrees during the drying process. The closer the contact angle is to 90 degrees, the smaller the stress generated in the patterns due to the surface tension of the organic solvent. Therefore, the collapse of patterns during the drying process can be suppressed.

[0113] Once a predetermined drying time has elapsed from the start of the drying process, the substrate holder 2 stops the rotation of the substrate W, and the first gas valve 33g closes. This effectively completes the drying process, and the series of processes on the substrate W is effectively finished.

[0114] Next, the substrate holding unit 2 releases its grip on the substrate W, and the second transport unit 122 removes the processed substrate W from the chamber 10 (step S9: unloading process).

[0115] <Effects> As described above, the processing unit 1 can perform processing on the substrate W. Furthermore, in the hydrophobic treatment, the processing unit 1 discharges hydrophobic liquid from the central nozzle 3h and the peripheral nozzle 4h. The hydrophobic liquid that lands on the central part of the substrate W can mainly hydrophobize the central part. By the time the hydrophobic liquid reaches the peripheral part of the substrate W, it may have already become inactive. For this reason, even if the hydrophobic liquid is continuously discharged only from the central nozzle 3h, the peripheral part of the substrate W will not be sufficiently hydrophobic. However, in this embodiment, the hydrophobic liquid from the peripheral nozzle 4 lands on the peripheral part of the substrate W. For this reason, the hydrophobic liquid that lands on the peripheral part of the substrate W can hydrophobize the peripheral part of the substrate W. Therefore, the entire main surface of the substrate W can be more appropriately hydrophobicized.

[0116] Furthermore, in the hydrophobic treatment, the hydrophobic flow rate ratio (=Fh1 / Fh2) decreases over time. For example, the hydrophobic flow rate ratio in period Th1 of the hydrophobic treatment period Th is higher than that in period Th2, and the hydrophobic flow rate ratio in period Th2 is higher than that in period Th3. Therefore, in the initial stages of the hydrophobic treatment (e.g., period Th1), a larger amount of hydrophobic solution can be applied to the central part of the substrate W. Initially, while organic solvent remains on the entire main surface of the substrate W, a relatively large amount of hydrophobic solution can push the organic solvent outwards from the center of the substrate W. Therefore, the organic solvent on the main surface of the substrate W can be replaced with the hydrophobic solution more quickly. In addition, the relatively large amount of hydrophobic solution can more quickly promote hydrophobicity in the central part of the main surface of the substrate W.

[0117] Furthermore, in the final stage of the hydrophobic treatment (for example, period Th3), a larger amount of hydrophobic solution can be applied to the peripheral area of ​​the substrate W. Therefore, the hydrophobicization of the peripheral area of ​​the main surface of the substrate W can be accelerated more rapidly by using a relatively large amount of hydrophobic solution.

[0118] For comparison, let's consider the case where the hydrophobic flow rate ratio is increased over time. In this case, during the initial part of the hydrophobic treatment period Th, a relatively small amount of hydrophobic solution lands on the central part of the substrate W, while a relatively large amount of hydrophobic solution lands on the peripheral part of the substrate W. The large amount of hydrophobic solution pushes the organic solvent on the peripheral part of the substrate W radially outward, but since the organic solvent flows from the central part to the peripheral part, the hydrophobic solution on the peripheral part is diluted by the organic solvent. As a result, the hydrophobic solution cannot act sufficiently on the peripheral part, and the hydrophobicization of the peripheral part of the substrate W may be insufficient. To sufficiently hydrophobize the peripheral part of the substrate W, it is necessary to lengthen the hydrophobic treatment period Th, which leads to a decrease in throughput and an increase in the amount of hydrophobic solution used. The amount of hydrophobic solution used here refers to the total amount of hydrophobic solution supplied to the substrate W throughout the entire hydrophobic treatment period Th.

[0119] In contrast, in this embodiment, the hydrophobic flow rate ratio is increased over time, allowing for the replacement of the organic solvent with the hydrophobic solution in a short time, and enabling the hydrophobicization of the entire main surface of the substrate W to be completed in a shorter time. As a result, the amount of hydrophobic solution used can also be reduced.

[0120] In the example shown in Figure 5, the first hydrophobic flow rate Fh1 during period Th1 is greater than the second hydrophobic flow rate Fh2. Therefore, the large amount of organic solvent remaining on the main surface of the substrate W in the initial stages of the hydrophobic treatment can be more quickly flushed out from the center by the hydrophobic solution. Also, in the example shown in Figure 5, the second hydrophobic flow rate Fh2 during period Th3 is greater than the first hydrophobic flow rate Fh1. Therefore, in the final stages of the hydrophobic treatment, the peripheral areas of the main surface of the substrate W can be hydrophobicized with a larger amount of hydrophobic solution. Consequently, the entire surface of the substrate W can be hydrophobicized more quickly.

[0121] Furthermore, in the example shown in Figure 5, the first hydrophobic flow rate Fh1 is greater than 0 throughout the entire hydrophobic treatment period Th. In other words, the central nozzle 3h discharges the hydrophobic solution towards the center of the main surface of the substrate W throughout the entire hydrophobic treatment period Th. As a result, the hydrophobic solution can cover the entire main surface of the substrate W, reducing the possibility of suspended matter in the chamber 10 adhering to the main surface of the substrate W.

[0122] Furthermore, in the example shown in Figure 5, the first hydrophobic flow rate Fh1 decreases over time, while the second hydrophobic flow rate Fh2 increases over time. Therefore, the time variation of the sum of the first hydrophobic flow rate Fh1 and the second hydrophobic flow rate Fh2 can be suppressed. Ideally, if the sum of the first hydrophobic flow rate Fh1 and the second hydrophobic flow rate Fh2 remains constant regardless of the passage of time, the time variation of this sum can be eliminated. If the time variation of the sum of the first hydrophobic flow rate Fh1 and the second hydrophobic flow rate Fh2 is small, it becomes easier to calculate and manage the supply amount of hydrophobic solution used in the hydrophobic treatment.

[0123] Figure 6 is a graph showing a second example of the time evolution of the first hydrophobic flow rate Fh1 and the second hydrophobic flow rate Fh2. In the example in Figure 6, the hydrophobic flow rate ratio (=Fh1 / Fh2) decreases with the passage of time. Specifically, the hydrophobic flow rate ratio in period Th1 is higher than the hydrophobic flow rate ratio in period Th2, and the hydrophobic flow rate ratio in period Th2 is higher than the hydrophobic flow rate ratio in period Th3. In the example in Figure 6, the first hydrophobic flow rate Fh1 is equal to the second hydrophobic flow rate Fh2 in period Th1, the first hydrophobic flow rate Fh1 is smaller than the second hydrophobic flow rate Fh2 in period Th2, and the first hydrophobic flow rate Fh1 is even smaller than the second hydrophobic flow rate Fh2 in period Th3.

[0124] Even in the example shown in Figure 6, since the hydrophobic flow rate ratio decreases over time, the entire main surface of the substrate W can be made hydrophobic in a shorter time compared to the case where the hydrophobic flow rate ratio increases over time.

[0125] In the example above, the first hydrophobic flow rate Fh1 and the second hydrophobic flow rate Fh2 are each changed in three stages over time, but they may also be changed in two stages, or in four or more stages. Alternatively, the first hydrophobic flow rate Fh1 and the second hydrophobic flow rate Fh2 may be changed continuously.

[0126] <Discharge direction of peripheral nozzle> Figure 7 is a schematic plan view showing an example of the configuration of the processing unit 1 according to the first embodiment. In the example in Figure 7, the substrate W is rotating counterclockwise. As shown in Figure 7, the peripheral nozzle 4h may discharge the hydrophobic liquid along the rotation direction of the substrate W in a plan view. In Figure 7, the discharge direction of the hydrophobic liquid discharged from the peripheral nozzle 4h is schematically shown by a solid straight arrow. As shown in Figure 7, the discharge direction of the hydrophobic liquid in a plan view of the peripheral nozzle 4h may be along the rotation direction of the liquid deposition position P1 on the main surface of the substrate W where the hydrophobic liquid discharged from the peripheral nozzle 4h is deposited. Specifically, the first angle between the discharge direction and the rotation direction at the liquid deposition position P1 is smaller than the second angle between the discharge direction and the radial direction at the liquid deposition position P1. The first angle may be, for example, a few degrees or less.

[0127] In the example in Figure 7, the direction of flow of the hydrophobic liquid deposited in the center of the main surface of the substrate W is schematically shown by arrows. In Figure 7, the portion overlapping with the central nozzle 3g and arm 351 is shown by a dashed line. The hydrophobic liquid flows radially outward while curving in the direction of rotation. Therefore, at the deposition position P1 on the periphery of the substrate W, the hydrophobic liquid flows radially outward and obliquely in the direction of rotation. At deposition position P1, the hydrophobic liquid from the peripheral nozzle 4h is deposited along the direction of rotation, so the hydrophobic liquid from the peripheral nozzle 4h and the hydrophobic liquid flowing along the main surface of the substrate W collide in a liquid flow direction that is closer to each other. Therefore, splashing of the hydrophobic liquid can be suppressed at deposition position P1. Splashing here refers to the rebound of fluid caused by collisions between fluids and collisions between fluids and the main surface of the substrate W. Suppression of splashing means, for example, a reduction in the distance between the main surface of the substrate W and the rebounded fluid.

[0128] For comparison, consider a structure in which the peripheral nozzle 4h discharges the hydrophobic liquid along the radial direction with respect to the rotation axis Q1. In Figure 4, this peripheral nozzle 4h is shown by a dashed line. In this structure, the hydrophobic liquid discharged from the peripheral nozzle 4h flows radially inward at the liquid application position P1. On the other hand, the hydrophobic liquid that lands in the center of the substrate W flows radially outward on the main surface of the substrate W. Therefore, these hydrophobic liquids collide at the liquid application position P1 in opposite liquid flow directions. As a result, splashing of the hydrophobic liquid is likely to occur at the liquid application position P1. If the hydrophobic liquid bounces significantly on the main surface of the substrate W, it may adhere to each component in the chamber 10. This situation is undesirable.

[0129] In contrast, in the example shown in Figure 7, the peripheral nozzle 4h discharges the hydrophobic liquid in a discharge direction along the rotational direction of the substrate W at the liquid application position P1. Therefore, splashing of the liquid can be suppressed, and the occurrence of the above-mentioned problem can be prevented.

[0130] <Length of the first and second periods> In the example shown in Figure 5, during period Th1, the hydrophobic liquid discharged at a larger first hydrophobic flow rate Fh1 hydrophobicizes the central part of the main surface of the substrate W. On the other hand, during period Th3, the hydrophobic liquid discharged at a larger second hydrophobic flow rate Fh2 hydrophobicizes the peripheral part of the main surface of the substrate W.

[0131] Incidentally, the length of the circumference around the axis of rotation Q1 increases as you move away from the axis of rotation Q1, that is, as the diameter of the circle increases. For this reason, the time required to supply sufficient hydrophobic solution to the peripheral part of the substrate W tends to be longer than the time required to supply sufficient hydrophobic solution to the central part of the substrate W. In particular, when the liquid application position P1 is located on a virtual circle with a diameter of 1 / √2 times or less the diameter of the substrate W, the area of ​​the peripheral part of the substrate W is larger than the area of ​​the central part. In this case, the time required to supply sufficient hydrophobic solution to the peripheral part of the substrate W becomes longer. Therefore, the length of period Th3 may be set to be longer than that of period Th1. For example, the period Th3 (corresponding to the second period) in which the second hydrophobic flow rate Fh2 is greater than the first hydrophobic flow rate Fh1 may be set to be longer than the period Th1 (corresponding to the first period) in which the first hydrophobic flow rate Fh1 is greater than the second hydrophobic flow rate Fh2. This allows for more appropriate hydrophobicization of the peripheral part of the substrate W.

[0132] <Rotation speed> The substrate holder 2 may change the rotation speed of the substrate W during the hydrophobic treatment period Th. For example, the substrate holder 2 may rotate the substrate W at a lower rotation speed during period Th3 than the rotation speed of the substrate W during period Th1. For example, the average value of the rotation speed of the substrate W during period Th3 may be set lower than the average value of the rotation speed of the substrate W during period Th1. The rotation speed may be set in advance and stored, for example, in the memory of the control unit 9.

[0133] Since the rotation speed of the substrate W is high during period Th1, the organic solvent initially remaining on the main surface of the substrate W can be removed more quickly. Also, during period Th1, hydrophobicization mainly occurs in the central part of the substrate W, and since each position in the central part of the substrate W is relatively close to the rotation axis Q1, the centrifugal force generated at each position is relatively small even at a high rotation speed, and the liquid film of the hydrophobic solution is relatively thick. For this reason, the central part of the substrate W can be hydrophobicized more appropriately during period Th1.

[0134] Furthermore, because the rotation speed of the substrate W is low during period Th3, the hydrophobic solution deposited on the periphery of the substrate W can remain on the periphery for a longer period. In other words, the centrifugal force acting on each point on the periphery of the substrate W can be reduced, and the film thickness of the hydrophobic solution on the periphery of the substrate W can be increased. For this reason, the periphery of the substrate W can be hydrophobic more effectively during period Th3.

[0135] <Second Embodiment> Figure 8 is a schematic diagram showing an example of the configuration of the processing unit 1 according to the second embodiment. Hereinafter, the processing unit 1 according to the second embodiment will also be referred to as processing unit 1A. In addition to the configuration of processing unit 1, processing unit 1A includes peripheral nozzles 4i and 4g as peripheral nozzles 4.

[0136] The peripheral nozzle 4i discharges the organic solvent as a fluid toward the peripheral edge of the main surface of the substrate W held by the substrate holding part 2. The peripheral nozzle 4i is, for example, a straight nozzle that discharges the organic solvent in a continuous flow state. As an example, the peripheral nozzle 4i discharges the organic solvent toward the upper surface of the substrate W. That is, the peripheral nozzle 4i is located above the substrate W held by the substrate holding part 2. As shown in Figure 8, the peripheral nozzle 4i may be provided radially outward from the substrate W in a plan view. The peripheral nozzle 4i may be fixed immovably to the chamber 10. That is, the peripheral nozzle 4i may be a fixed nozzle. The peripheral nozzle 4i discharges the organic solvent, for example, along an oblique downward direction. The hydrophobic liquid discharged from the peripheral nozzle 4i lands on the peripheral edge of the main surface of the substrate W.

[0137] The downstream end of the second solvent pipe 41i is connected to the peripheral nozzle 4i. The upstream end of the second solvent pipe 41i is connected to an organic solvent supply source (not shown). The second solvent control valve 42i is inserted into the second solvent pipe 41i. The second solvent control valve 42i adjusts the flow rate of the organic solvent flowing through the second solvent pipe 41i, that is, the flow rate of the organic solvent discharged from the peripheral nozzle 4i. Hereinafter, the flow rate of the organic solvent flowing through the second solvent pipe 41i, that is, the flow rate of the organic solvent discharged from the peripheral nozzle 4i, will be referred to as the second solvent flow rate Fi2, and the flow rate of the organic solvent flowing through the first solvent pipe 31i, that is, the flow rate of the organic solvent discharged from the central nozzle 3i, will be referred to as the first solvent flow rate Fi1.

[0138] The first solvent control valve 32i and the second solvent control valve 42i are controlled by the control unit 9. In other words, the control unit 9 controls the first solvent control valve 32i and the second solvent control valve 42i to discharge organic solvent from the central nozzle 3i and the peripheral nozzle 4i at the first solvent flow rate Fi1 and the second solvent flow rate Fi2, respectively.

[0139] In the example shown in Figure 8, a second solvent on-off valve 43i is inserted into the second solvent pipe 41i. The second solvent on-off valve 43i switches the flow path of the second solvent pipe 41i open and closed. The second solvent on-off valve 43i is controlled by the control unit 9.

[0140] When at least one of the first solvent valve 33i and the second solvent valve 43i opens, the organic solvent is supplied to the main surface of the substrate W. Hereinafter, the processing period during which the organic solvent is supplied to the substrate W will also be referred to as the solvent processing period Ti.

[0141] During the solvent treatment period Ti, the control unit 9 controls the first solvent control valve 32i and the second solvent control valve 42i to change the ratio of the first solvent flow rate Fi1 to the second solvent flow rate Fi2 (=Fi1 / Fi2) over time. Hereinafter, this ratio will be referred to as the solvent flow rate ratio. As a more specific example, the control unit 9 makes the solvent flow rate ratio during the first solvent period, which is part of the solvent treatment period, higher than the solvent flow rate ratio during the second solvent period, which is later than the first solvent period within the solvent treatment period. The technical significance of this will be explained in detail later.

[0142] The peripheral nozzle 4g ​​discharges inert gas as a fluid toward the peripheral edge of the main surface of the substrate W held by the substrate holding part 2. For example, the peripheral nozzle 4g ​​discharges inert gas toward the upper surface of the substrate W. That is, the peripheral nozzle 4g ​​is located above the substrate W held by the substrate holding part 2. As shown in Figure 8, the peripheral nozzle 4g ​​may be provided radially outward from the substrate W in a plan view. The peripheral nozzle 4g ​​may be fixed immovably to the chamber 10. That is, the peripheral nozzle 4g ​​may be a fixed nozzle. The peripheral nozzle 4g ​​discharges inert gas, for example, along an oblique downward direction. The inert gas discharged from the peripheral nozzle 4g ​​collides with the peripheral edge of the main surface of the substrate W.

[0143] The downstream end of the second gas pipe 41g is connected to the peripheral nozzle 4g. The upstream end of the second gas pipe 41g is connected to a gas supply source (not shown). The second gas control valve 42g is inserted into the second gas pipe 41g. The second gas control valve 42g adjusts the flow rate of inert gas flowing through the second gas pipe 41g, that is, the flow rate of inert gas discharged from the peripheral nozzle 4g. Hereinafter, the flow rate of inert gas flowing through the second gas pipe 41g, that is, the flow rate of inert gas discharged from the peripheral nozzle 4g, will be referred to as the second gas flow rate Fg2, and the flow rate of inert gas flowing through the first gas pipe 31g, that is, the flow rate of inert gas discharged from the central nozzle 3g, will be referred to as the first gas flow rate Fg1.

[0144] The first gas regulating valve 32g and the second gas regulating valve 42g are controlled by the control unit 9. In other words, the control unit 9 controls the first gas regulating valve 32g and the second gas regulating valve 42g to discharge inert gas from the central nozzle 3g and the peripheral nozzle 4g ​​at the first gas flow rate Fg1 and the second gas flow rate Fg2, respectively.

[0145] In the example shown in Figure 8, a second gas on-off valve 43g is inserted into the second gas pipe 41g. The second gas on-off valve 43g switches the flow path of the second gas pipe 41g open and closed. The second gas on-off valve 43g is controlled by the control unit 9.

[0146] When at least one of the first gas valve 33g and the second gas valve 43g opens, an inert gas is supplied to the main surface of the substrate W. Hereinafter, the processing period during which the inert gas is supplied to the substrate W will also be referred to as the gas processing period.

[0147] The control unit 9 may control the ratio of the first gas flow rate Fg1 to the second gas flow rate Fg2 (=Fg1 / Fg2) to keep constant during the gas processing period.

[0148] <An example of the operation of a substrate processing device> An example of the operation of processing unit 1A is the same as in Figure 3. However, in at least one of the pre-solvent treatment (step S5) and post-solvent treatment (step S7), the control unit 9 opens the first solvent on / off valve 33i and the second solvent on / off valve 43i. As a result, the central nozzle 3i and the peripheral nozzle 4i discharge organic solvent at the first solvent flow rate Fi1 and the second solvent flow rate Fi2, respectively. During the solvent treatment period Ti, the control unit 9 controls the first solvent control valve 32i and the second solvent control valve 42i to change the solvent flow rate ratio (=Fi1 / Fi2) according to the passage of time. The sum of the first solvent flow rate Fi1 and the second solvent flow rate Fi2 is set to be greater than, for example, the sum of the first hydrophobic flow rate Fh1 and the second hydrophobic flow rate Fh2. The sum of the first solvent flow rate Fi1 and the second solvent flow rate Fi2 is set to be, for example, 200 ccm or more and 400 ccm or less, and as a more specific example, it is set to be 300 ccm.

[0149] Figure 9 is a schematic diagram showing an example of the state of the processing unit 1 during pre-solvent treatment or post-solvent treatment, and Figure 10 is a graph showing an example of the time change of the first solvent flow rate Fi1 and the second solvent flow rate Fi2. In the example of Figure 10, the solvent treatment period Ti consists of periods Ti1, Ti2, and Ti3. Here, period Ti2 is the period following period Ti1, and period Ti3 is the period following period Ti2. Figure 9(a) shows an example of the state of the processing unit 1A during period Ti1, Figure 9(b) shows an example of the state of the processing unit 1A during period Ti2, and Figure 9(c) shows an example of the state of the processing unit 1A during period Ti3. In the examples of Figures 9(a) to 9(c), the magnitude of the first solvent flow rate Fi1 of the organic solvent discharged from the central nozzle 3i and the second solvent flow rate Fi2 of the organic solvent discharged from the peripheral nozzle 4i are schematically shown by the width of the liquid column of organic solvent.

[0150] As shown in Figures 9 and 10, the control unit 9 makes the solvent flow rate ratio (=Fi1 / Fi2) in period Ti1 higher than the solvent flow rate ratio in period Ti2, and makes the solvent flow rate ratio in period Ti2 higher than the solvent flow rate ratio in period Th3. In other words, the control unit 9 controls the first solvent control valve 32i and the second solvent control valve 42i so that the solvent flow rate ratio decreases over time. The solvent flow rate ratio in period Ti1 may be, for example, 1.5 or more. The second solvent flow rate Fi2 in period Ti1 may be zero. The solvent flow rate ratio in period Ti2 may be, for example, 0.8 or more and less than 1.5. The solvent flow rate ratio in period Ti3 may be, for example, 0.01 or more and less than 0.8.

[0151] An example of the time variation of the first solvent flow rate Fi1 is the same as that of the first hydrophobic flow rate Fh1, an example of the time variation of the second solvent flow rate Fi2 is the same as that of the second hydrophobic flow rate Fh2, and an example of the time variation of the relative magnitudes of the first solvent flow rate Fi1 and the second solvent flow rate Fi2 is the same as that of the relative magnitudes of the first hydrophobic flow rate Fh1 and the second hydrophobic flow rate Fh2.

[0152] As described above, the processing unit 1A discharges organic solvent from the central nozzle 3i and the peripheral nozzle 4i during at least one of the pre-solvent treatment and post-solvent treatment. The liquid film of organic solvent that adheres to the central part of the substrate W becomes thinner towards the peripheral part of the substrate W, but organic solvent also adheres to the peripheral part of the substrate W. As a result, the entire main surface of the substrate W is more reliably covered with organic solvent. Therefore, the possibility of airborne particles in the chamber 10 adhering to the main surface of the substrate W can be reduced.

[0153] Furthermore, during the solvent treatment period Ti, the solvent flow rate ratio (=Fh1 / Fh2) decreases with the passage of time. Therefore, during the first solvent treatment period (e.g., period Ti1) of the solvent treatment period Ti, a larger amount of organic solvent can be deposited in the central part of the substrate W. During the first solvent treatment period, while the rinse solution or hydrophobic solution remains on the entire main surface of the substrate W, a relatively large amount of organic solvent can push the rinse solution or hydrophobic solution outwards from the central part of the substrate W. Therefore, the liquid on the main surface of the substrate W can be replaced with the organic solvent more quickly. In particular, the relatively large amount of organic solvent can promote the replacement of the liquid with the organic solvent in the central part of the main surface of the substrate W. In other words, the liquid in the central part of the substrate W can be replaced with the organic solvent in a shorter time. Also, since a larger amount of organic solvent is deposited in the central part of the substrate W, the replacement of the liquid with the organic solvent can be promoted even between the patterns in the central part of the substrate W.

[0154] Furthermore, during the second solvent treatment period (e.g., period Ti3) following the first solvent treatment period Ti, a larger amount of organic solvent can be applied to the peripheral edges of the substrate W. Therefore, the relatively large amount of organic solvent can promote the substitution of the main surface of the substrate W with the organic solvent at its peripheral edges. Consequently, substitution of the organic solvent can also be promoted between the patterns at the peripheral edges of the substrate W.

[0155] As described above, according to the second embodiment, the liquid on the main surface of the substrate W can be replaced with an organic solvent in an order corresponding to the radial outward flow of the liquid on the substrate W (from the center to the periphery). Therefore, the entire main surface of the substrate W can be covered with liquid, while the replacement of the entire main surface of the substrate W with an organic solvent can be performed in a shorter time. As a result, the amount of organic solvent used can also be reduced.

[0156] In the example shown in Figure 10, the flow rate of the first solvent Fi1 during period Ti1 is greater than the flow rate of the second solvent Fi2. Therefore, the large amount of liquid remaining on the main surface of the substrate W in the early stages of the solvent treatment period Ti can be more quickly flushed away with the organic solvent. Also, in the example shown in Figure 10, the flow rate of the second solvent Fi2 during period Ti3 is greater than the flow rate of the first solvent Fi1. Therefore, in the later stages of the solvent treatment period Ti, a larger amount of liquid on the peripheral edges of the main surface of the substrate W can be flushed away with the organic solvent.

[0157] Furthermore, in the example shown in Figure 10, the first solvent flow rate Fi1 decreases over time, while the second solvent flow rate Fi2 increases over time. Therefore, the time variation of the sum of the first solvent flow rate Fi1 and the second solvent flow rate Fi2 can be suppressed. Ideally, if the sum of the first solvent flow rate Fi1 and the second solvent flow rate Fi2 remains constant regardless of the passage of time, the time variation of this sum can be eliminated. If the time variation of the sum of the first solvent flow rate Fi1 and the second solvent flow rate Fi2 is small, it becomes easier to calculate and manage the supply amount of organic solvent used in pre-solvent treatment or post-solvent treatment.

[0158] In the second embodiment, during the drying process (step S8), the central nozzle 3g and the peripheral nozzle 4g ​​may supply inert gas. That is, the control unit 9 may open the first gas shut-off valve 33g and the second gas shut-off valve 43g during the drying process. Hereinafter, the period during which inert gas is supplied to the substrate W will also be referred to as the gas treatment period. During the drying process, the control unit 9 may control the flow rate (target value) of the inert gas from the central nozzle 3g and the peripheral nozzle 4g ​​to be constant regardless of the passage of time. For example, the control unit 9 may control the opening degree of the first gas regulating valve 32g and the second gas regulating valve 42g to be constant during the gas treatment period.

[0159] During the drying process, the inert gas collides with both the central and peripheral parts of the substrate W, which promotes the vaporization or blowing away of organic solvents on the main surface of the substrate W. Therefore, the processing unit 1A can complete the drying process in a shorter time.

[0160] Furthermore, by controlling the opening degrees of the first gas control valve 32g and the second gas control valve 42g to a constant level during the gas processing period, the processing load on the control unit 9 can be reduced.

[0161] Alternatively, the control unit 9 may reduce the gas flow rate ratio of the first gas flow rate Fg1 to the second gas flow rate Fg2 (=Fg1 / Fg2) over time during the gas processing period. An example of the time change of the gas flow rate ratio is the same as that of the hydrophobic flow rate ratio, an example of the time change of the first gas flow rate Fg1 is the same as that of the first hydrophobic flow rate Fh1, and an example of the time change of the second gas flow rate Fg2 is the same as that of the second hydrophobic flow rate Fh2. Furthermore, an example of the time change of the relative magnitudes of the first gas flow rate Fg1 and the second gas flow rate Fg2 is the same as that of the relative magnitudes of the first hydrophobic flow rate Fh1 and the second hydrophobic flow rate Fh2.

[0162] According to this, a larger amount of inert gas is supplied to the center of the substrate W at the beginning of the drying process. This promotes the vaporization or radial outward extrusion of the organic solvent in the center of the substrate W. On the other hand, a larger amount of inert gas is supplied to the periphery of the substrate W at the end of the drying process. This promotes the vaporization or radial outward extrusion of the organic solvent in the periphery of the substrate W. In other words, the main surface of the substrate W can be dried in an order corresponding to the radial outward flow of the organic solvent on the substrate W (from the center to the periphery). As a result, the processing unit 1A can complete the drying process in a shorter time. In addition, the amount of inert gas used can be reduced.

[0163] <Discharge direction of peripheral nozzle> Figure 11 is a schematic plan view showing an example of the configuration of a processing unit 1A according to a second embodiment. In the example in Figure 11, the substrate W is rotating counterclockwise. As shown in Figure 11, the peripheral nozzle 4i may discharge the organic solvent in line with the rotation direction of the substrate W in a plan view. That is, the discharge direction of the organic solvent from the peripheral nozzle 4i in a plan view may be in line with the rotation direction of the organic solvent discharged from the peripheral nozzle 4i at the point of contact on the main surface of the substrate W. More specifically, the first solvent angle between the discharge direction and the rotation direction at the point of contact is smaller than the second solvent angle between the discharge direction and the radial direction at the point of contact. The first solvent angle may be, for example, a few degrees or less.

[0164] With this structure, splashing of the organic solvent can be suppressed, as can splashing of the hydrophobic liquid at the peripheral nozzle 4h.

[0165] Furthermore, as shown in Figure 11, the peripheral nozzle 4g ​​may discharge inert gas along the rotational direction of the substrate W in a plan view. That is, the discharge direction of the inert gas from the peripheral nozzle 4g ​​in a plan view may be along the rotational direction at the point of impact of the inert gas discharged from the peripheral nozzle 4g ​​on the main surface of the substrate W. More specifically, the first gas angle between the discharge direction and the rotational direction at the impact point is smaller than the second gas angle between the discharge direction and the radial direction at the impact point. The first gas angle may be, for example, a few degrees or less.

[0166] Now, the inert gas discharged from the central nozzle 3g flows in an arc that curves radially outward and in the direction of rotation as the substrate W rotates. In other words, the inert gas also flows in the same direction as the hydrophobic liquid in Figure 7. Therefore, the inert gas discharged from the peripheral nozzle 4g ​​collides with the arc-shaped flowing inert gas at the collision point in airflow directions that are close to each other. Consequently, turbulence of the inert gas airflow at the collision point can be suppressed.

[0167] If large turbulence occurs, it may cause the organic solvent on the substrate W to be stirred up more than necessary, or guide suspended matter in the chamber 10 to the main surface of the substrate W. Such a situation is undesirable. In contrast, the structure shown in Figure 11 can suppress the generation of turbulence, and therefore the occurrence of the above-mentioned situations can be prevented.

[0168] <Third Embodiment> Figure 12 is a schematic plan view showing an example of the configuration of the processing unit 1 according to the third embodiment. Hereinafter, the processing unit 1 according to the third embodiment will be referred to as processing unit 1B.

[0169] Processing unit 1B has the same configuration as processing unit 1A, except for the presence or absence of a nozzle moving mechanism 45 for moving the peripheral nozzle 4. The nozzle moving mechanism 45 moves the peripheral nozzle 4 between the peripheral processing position and the peripheral standby position, which will be described below. The peripheral processing position is the position in which the peripheral nozzle 4 discharges fluid toward the peripheral edge of the main surface of the substrate W held by the substrate holding part 2, for example, a position that is perpendicular to the peripheral edge of the substrate W. The peripheral standby position is the position in which the peripheral nozzle 4 does not discharge fluid toward the substrate W, for example, a position radially outside the substrate W. In the example in Figure 12, the peripheral nozzle 4 that stops at the peripheral standby position is shown by a solid line, and the peripheral nozzle 4 that stops at the peripheral processing position is shown by a dashed line.

[0170] In the example shown in Figure 12, the nozzle moving mechanism 45 includes an arm 451, a support column 452, and a drive source 453. The support column 452 is located radially outward from the guard portion 7 and extends vertically. The arm 451 extends horizontally, its tip connected to the peripheral nozzle 4, and its base connected to the support column 452. The drive source 453 rotates the support column 452 around its central axis Q3. The drive source 453 includes, for example, a motor. As the support column 452 rotates around the central axis Q3, the peripheral nozzle 4 moves along the circumferential direction with respect to the central axis Q3. The support column 452 is installed such that the peripheral processing position and peripheral standby position are located on the movement trajectory of the peripheral nozzle 4. Note that the nozzle moving mechanism 45 is not necessarily limited to the embodiment shown in Figure 12, and may include, for example, a linear motion mechanism such as a linear motor.

[0171] As shown in Figure 12, the nozzle moving mechanism 45 may move the peripheral nozzles 4h, 4i, and 4g together. In the example in Figure 12, the peripheral nozzles 4h, 4i, and 4g are connected to the tip of the arm 451. The peripheral nozzles 4h, 4i, and 4g are adjacent to each other in the horizontal direction, and as a specific example, they are aligned along the longitudinal direction of the arm 451.

[0172] <An example of the operation of a substrate processing device> An example of the operation of the processing unit 1B according to the third embodiment is the same as in the second embodiment. However, in the pre-solvent treatment (step S5), hydrophobic treatment (step S6), post-solvent treatment (step S7), and drying treatment (step S8), the nozzle moving mechanism 45 positions the peripheral nozzle 4 at the peripheral treatment position.

[0173] Figure 13 is a schematic diagram showing an example of the processing unit 1B during hydrophobic treatment. As shown in Figure 13, during the hydrophobic treatment, the peripheral nozzle 4h is located at a peripheral treatment position that is perpendicular to the peripheral edge of the main surface of the substrate W. At this time, the peripheral nozzle 4 is aligned horizontally with the central nozzle 3. Because the peripheral nozzle 4h is located at the peripheral treatment position, during the hydrophobic treatment, the peripheral nozzle 4h can discharge the hydrophobic liquid from a position closer to the main surface of the substrate W toward the peripheral edge of the main surface of the substrate W. Therefore, splashing of the hydrophobic liquid on the main surface of the substrate W can be suppressed.

[0174] Similarly, in both the pre-solvent treatment and the post-solvent treatment, the peripheral nozzle 4i can discharge the organic solvent from a position closer to the main surface of the substrate W toward the peripheral edge of the main surface of the substrate W. This suppresses splashing of the organic solvent onto the main surface of the substrate W.

[0175] Furthermore, during the drying process, the peripheral nozzle 4g ​​can discharge inert gas from a position closer to the main surface of the substrate W towards the peripheral edge of the main surface of the substrate W. Therefore, the inert gas from the peripheral nozzle 4g ​​can collide with the main surface of the substrate W at a higher flow rate. Consequently, organic solvents between patterns can be blown away to the outside of the patterns.

[0176] Each peripheral nozzle 4 may discharge the fluid downward along the vertical direction, or it may discharge the fluid in an oblique direction that moves radially outward as it moves vertically downward. For example, peripheral nozzle 4h may discharge the hydrophobic liquid along this oblique direction. In the example in Figure 13, this oblique direction is schematically shown by a dashed arrow. According to this, the hydrophobic liquid from peripheral nozzle 4 collides with the hydrophobic liquid flowing radially outward from the center of the substrate W in similar liquid flow directions. Therefore, splashing of the hydrophobic liquid can be further suppressed. Splashing of the organic solvent discharged from peripheral nozzle 4i can also be further suppressed. In addition, the inert gas from peripheral nozzle 4g ​​collides with the inert gas from central nozzle 3g in similar airflow directions, so the generation of turbulence can be suppressed.

[0177] Furthermore, although peripheral nozzles 4h, 4i, and 4g are provided as peripheral nozzles 4, similar to the first embodiment, only peripheral nozzle 4h may be provided.

[0178] As described above, the substrate processing apparatus 100 and the substrate processing method have been described in detail, but the above description is illustrative in all respects, and this disclosure is not limited thereto. Furthermore, the various modifications described above can be applied in combination as long as they do not contradict each other. And it is understood that a number of modifications not illustrated can be conceivable without falling outside the scope of this disclosure.

[0179] In the example described above, each fluid is provided with its own dedicated nozzle, but a single nozzle may be shared by different types of fluids.

[0180] Furthermore, in the example described above, the central nozzle 3g discharges inert gas toward the upper surface of the substrate W, but it may also discharge inert gas radially outward. For example, a first internal flow path and a second internal flow path are formed inside the central nozzle 3g. The first internal flow path extends vertically and opens at the lower surface of the central nozzle 3g. The second internal flow path is formed around the first internal flow path and opens at the outer circumferential surface of the central nozzle 3g. The second internal flow path may open around the entire circumference of the outer circumferential surface of the central nozzle 3g. The first and second internal flow paths of the central nozzle 3g are connected to the first gas pipe 31g. The inert gas flowing into the first internal flow path flows out from the opening at the lower surface of the central nozzle 3g toward the upper surface of the substrate W. The inert gas flowing into the second internal flow path flows out radially outward from the opening at the outer circumferential surface of the central nozzle 3g. As a result, the inert gas flowing out from the outer circumferential surface of the central nozzle 3g can cover the substrate W above it. This allows the substrate W to be dried while more reliably protecting its upper surface during the drying process.

[0181] Furthermore, in the example described above, although the central nozzle 3g and peripheral nozzle 4g ​​discharge inert gas during the drying process (step S8), they may also discharge inert gas during other processes (e.g., hydrophobic treatment). [Explanation of Symbols]

[0182] 2 Board holding part 3,3i,3g,3h central nozzle 31i First solvent tube 31g First gas pipe 31h First drainage pipe 32i First solvent control valve 32g No. 1 gas regulating valve 32h First hydrophobic control valve 4,4i,4g,4h Peripheral nozzle 41i Second solvent pipe 41g Second gas pipe 41h Second drainage pipe 42i Second solvent control valve 42g Second gas regulating valve 42h Second hydrophobic control valve 9. Control Unit Fi1 First solvent flow rate Fi2 Second solvent flow rate Fh1 First hydrophobic flow rate Fh2 Second hydrophobic flow rate

Claims

1. A substrate holding part that rotates the substrate while holding it, At least one central nozzle that discharges fluid toward the center of the main surface of the substrate held by the substrate holding portion, A first hydrophobic pipe for supplying the hydrophobic liquid, which is the fluid, to the central nozzle, A first hydrophobic adjustment valve for adjusting the first hydrophobic flow rate of the hydrophobic liquid flowing through the first hydrophobic pipe, At least one peripheral nozzle that discharges fluid toward the peripheral edge of the main surface of the substrate held by the substrate holding portion, A second hydrophobic pipe for supplying the hydrophobic liquid, which is the fluid, to the peripheral nozzle, A second hydrophobic control valve adjusts the second hydrophobic flow rate of the hydrophobic liquid flowing through the second hydrophobic pipe, A control unit that controls the first hydrophobic regulating valve and the second hydrophobic regulating valve to adjust the hydrophobic flow rate ratio of the first hydrophobic flow rate to the second hydrophobic flow rate, and Equipped with, A substrate processing apparatus comprising a control unit that makes the hydrophobic flow rate ratio during a first period of hydrophobic treatment, in which a hydrophobic liquid is supplied to the main surface of the substrate, higher than the hydrophobic flow rate ratio during a second period following the first period of hydrophobic treatment.

2. A substrate processing apparatus according to claim 1, A substrate processing apparatus comprising a control unit that controls the first hydrophobic control valve and the second hydrophobic control valve to make the first hydrophobic flow rate during the first period greater than the second hydrophobic flow rate during the first period, and the first hydrophobic flow rate during the second period less than the second hydrophobic flow rate during the second period.

3. A substrate processing apparatus according to claim 1 or claim 2, A substrate processing apparatus comprising a control unit that controls the first hydrophobic control valve and the second hydrophobic control valve to make the first hydrophobic flow rate in the first period greater than the first hydrophobic flow rate in the second period, and the second hydrophobic flow rate in the first period less than the second hydrophobic flow rate in the second period.

4. A substrate processing apparatus according to claim 3, A substrate processing apparatus comprising a control unit that controls the first hydrophobic regulating valve and the second hydrophobic regulating valve to make the sum of the first hydrophobic flow rate and the second hydrophobic flow rate in the first period equal to the sum of the first hydrophobic flow rate and the second hydrophobic flow rate in the second period.

5. A substrate processing apparatus according to claim 1 or claim 2, A substrate processing apparatus wherein the second period is longer than the first period.

6. A substrate processing apparatus according to claim 1 or claim 2, A substrate processing apparatus wherein the rotation speed of the substrate during the second period is lower than the rotation speed of the substrate during the first period.

7. A substrate processing apparatus according to claim 1 or claim 2, The peripheral nozzle is a fixed nozzle, and in a plan view, it discharges the hydrophobic liquid in a direction along the rotational direction of the substrate, in a substrate processing apparatus.

8. A substrate processing apparatus according to claim 1 or claim 2, A substrate processing apparatus further comprising a nozzle moving mechanism for moving the peripheral nozzle between a peripheral processing position facing the peripheral portion of the main surface of the substrate and a peripheral standby position radially outward from the substrate.

9. A substrate processing apparatus according to claim 1 or claim 2, A first solvent pipe connected to the at least one central nozzle for supplying the organic solvent as the fluid to the at least one central nozzle, A first solvent control valve is inserted into the first solvent pipe and adjusts the first solvent flow rate of the organic solvent flowing through the first solvent pipe, A second solvent pipe connected to the at least one peripheral nozzle for supplying the organic solvent as the fluid to the at least one peripheral nozzle, A second solvent control valve is inserted into the second solvent pipe and adjusts the flow rate of the second solvent of the organic solvent flowing through the second solvent pipe. Furthermore, The control unit, The first solvent control valve and the second solvent control valve are controlled to adjust the solvent flow rate ratio of the first solvent flow rate to the second solvent flow rate, A substrate processing apparatus that makes the solvent flow rate ratio during a first solvent period of a solvent treatment period in which an organic solvent is supplied to the substrate higher than the solvent flow rate ratio during a second solvent period that is later than the first solvent period of the solvent treatment period.

10. A substrate processing apparatus according to claim 9, A substrate processing apparatus wherein the sum of the first hydrophobic flow rate and the second hydrophobic flow rate is less than the sum of the first solvent flow rate and the second solvent flow rate.

11. A substrate processing apparatus according to claim 1 or claim 2, A first gas pipe connected to the at least one central nozzle for supplying the inert gas as the fluid to the at least one central nozzle, A first gas control valve is inserted into the first gas pipe and adjusts the first gas flow rate of the inert gas flowing through the first gas pipe, A second gas pipe connected to the at least one peripheral nozzle for supplying the inert gas as the fluid to the at least one peripheral nozzle, A second gas control valve is inserted into the second gas pipe and adjusts the flow rate of the second inert gas flowing through the second gas pipe. A substrate processing device further equipped with these features.

12. A substrate processing apparatus according to claim 11, The control unit controls the opening degrees of the first gas control valve and the second gas control valve to a constant value during a gas treatment period in which an inert gas is supplied to the substrate, in a substrate processing apparatus.

13. (a) A step of holding the substrate, (b) A step in which, while rotating the substrate, the central nozzle discharges the hydrophobic liquid toward the central part of the main surface of the substrate, and the peripheral nozzle discharges the hydrophobic liquid toward the peripheral part of the main surface of the substrate. Equipped with, In step (b) above, A substrate processing method comprising making the ratio of the hydrophobic flow rate of the hydrophobic liquid applied to the central part of the main surface of the substrate to the ratio of the hydrophobic flow rate of the hydrophobic liquid applied to the peripheral part of the main surface of the substrate to the ratio of the hydrophobic flow rate of the hydrophobic liquid applied to the central part of the main surface of the substrate smaller in a second period following the first period than in a first period.

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