Substrate processing method and substrate processing system

Abstract

The invention provides a technique for adjusting the exposure sensitivity of a resist film. A substrate processing method is provided. The method includes: a step (a) of providing a substrate (ST1) having a base film; and a step (b) in which a metal-containing resist film (ST2) is formed on the base film. The step (b) includes: a step (b1) in which a first resist film (ST21) containing a metal is formed on the base film; and a step (b2) for forming, on the first resist film, a second resist film (ST22) containing a metal at a composition ratio different from that of the first resist film.

Description

Technical Field

[0001] Exemplary embodiments of the present invention relate to a substrate processing method and a substrate processing system. Background Art

[0002] Patent Document 1 discloses a technology for forming a thin film on a semiconductor substrate that can be patterned using extreme ultraviolet light (hereinafter referred to as “EUV light”).

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application No. 2021-523403 Summary of the invention

[0006] Technical problem to be solved by the invention

[0007] The present invention provides a technology for adjusting the exposure sensitivity of a resist film.

[0008] Technical means of solving problems

[0009] In an exemplary embodiment of the present invention, a substrate processing method is provided, comprising: step (a), providing a substrate having a base film; and step (b), forming a metal-containing resist film on the base film, wherein the step (b) comprises: step (b1), forming a first resist film containing a metal on the base film; and step (b2), forming a second resist film containing the metal in a composition ratio different from that of the first resist film on the first resist film.

[0010] Effects of the Invention

[0011] According to an exemplary embodiment of the present invention, it is possible to provide a technique for adjusting the exposure sensitivity of a resist film. BRIEF DESCRIPTION OF THE DRAWINGS

[0012] Figure 1 It is a diagram for explaining a configuration example of a heat treatment system.

[0013] Figure 2 It is a diagram for explaining a configuration example of a plasma processing system.

[0014] Figure 3 It is a diagram for explaining a configuration example of a capacitive coupling type plasma processing apparatus.

[0015] Figure 4 It is a diagram for explaining a configuration example of a liquid processing system.

[0016] Figure 5is a flow chart showing the present processing method.

[0017] Figure 6 FIG. 1 is a diagram showing an example of a base film UF of a substrate W. FIG.

[0018] Figure 7 FIG. 1 is a diagram showing an example of a base film UF of a substrate W. FIG.

[0019] Figure 8 It is a diagram showing an example of the cross-sectional structure of the substrate W on which the first resist film RM1 is formed.

[0020] Fig. 9 This is a flowchart showing an example of step ST21 using the ALD method.

[0021] Fig.10 This is a diagram schematically showing an example of a phenomenon occurring on the surface of the substrate W in the step ST21 using the ALD method.

[0022] Fig.11 It is a diagram showing an example of the cross-sectional structure of the substrate W on which the second resist film RM2 is formed.

[0023] Fig.12 It is a block diagram for explaining a configuration example of a substrate processing system SS.

[0024] Fig.13 is a flow chart representing method MT. DETAILED DESCRIPTION

[0025] Hereinafter, each embodiment of the present invention will be described.

[0026] In an exemplary embodiment, a substrate processing method is provided, comprising: step (a) of providing a substrate having a base film; and step (b) of forming a metal-containing resist film on the base film, wherein step (b) comprises: step (b1) of forming a first resist film containing metal on the base film; and step (b2) of forming a second resist film containing metal at a composition ratio different from that of the first resist film on the first resist film.

[0027] In one exemplary embodiment, the composition ratio of the metal in the second resist film is lower than the composition ratio of the metal in the first resist film.

[0028] In one exemplary embodiment, the metal-containing resist film includes at least one metal selected from the group consisting of Sn, Hf, and Ti.

[0029] In one exemplary embodiment, the metal-containing film is formed such that the composition ratio of the metal changes stepwise or continuously as going upward from the base film.

[0030] In an exemplary embodiment, step (b1) and step (b2) each include a step of coating a solution on a substrate, and the metal composition ratio of the metal-containing precursor in the solution used in step (b2) is lower than the metal composition ratio of the metal-containing precursor in the solution used in step (b1).

[0031] In one exemplary embodiment, the step (b1) includes a step of heating the substrate coated with the solution.

[0032] In one exemplary embodiment, the step (b2) includes a step of heating the substrate coated with the solution.

[0033] In an exemplary embodiment, step (b1) and step (b2) each include a step of providing a mixed gas containing a metal-containing gas and an oxidizing gas to the substrate, and the ratio of the flow rate of the metal-containing gas to the total flow rate of the mixed gas or the total flow rate of the mixed gas is lower in step (b2) than in step (b1).

[0034] In an exemplary embodiment, step (b1) and step (b2) each include the step of alternately supplying a first gas containing a metal-containing gas and a second gas containing an oxidizing gas, and a ratio of a flow rate of the first gas to a flow rate of the second gas or a total flow rate of the first gas and the second gas is lower in step (b2) than in step (b1).

[0035] In an exemplary embodiment, the metal-containing gas comprises a metal-containing organic precursor.

[0036] In an exemplary embodiment, the oxidizing gas includes at least one selected from the group consisting of H2O gas, H2O2 gas, O3 gas, and O2 gas.

[0037] In one exemplary embodiment, in step (a), the substrate is provided on a substrate support, and the temperature of the substrate support in step (b2) is lower than the temperature of the substrate support in step (b1).

[0038] In one exemplary embodiment, the step (b1) includes a step of heating the substrate.

[0039] In one exemplary embodiment, the step (b2) includes a step of heating the substrate.

[0040] In one exemplary embodiment, step (b) includes a step (b3) of forming one or more resist films containing a metal at a composition ratio different from that of the first resist film and the second resist film on the second resist film.

[0041] In one exemplary embodiment, the method further includes a step (c) of heating the substrate after the step (b).

[0042] In one exemplary embodiment, the method further includes step (d) of exposing the substrate after step (b) to form an exposed first region and an unexposed second region on the metal-containing resist film.

[0043] In one exemplary embodiment, the method further includes a step (e) of developing the substrate after the step (d) to selectively remove the second region from the metal-containing resist film.

[0044] In an exemplary embodiment, a substrate processing method is provided, comprising: step (a), providing a substrate, wherein the substrate has a base film and a metal-containing resist film on the base film, the metal-containing resist film comprising a first resist film containing metal on the base layer, and a second resist film on the first resist film containing the metal in a composition ratio different from that of the first resist film, the metal-containing resist film comprising an exposed first area and an unexposed second area; and step (b), developing the substrate to selectively remove the second area from the metal-containing resist film.

[0045] In one exemplary embodiment, the method further includes a step (f) of etching the base film after developing the substrate to selectively remove the second region from the metal-containing resist film.

[0046] In an exemplary embodiment, a substrate processing system is provided, comprising one or more substrate processing devices and a control unit, wherein the control unit is configured to enable the one or more substrate processing devices to perform control including control (a) and control (b), wherein in control (a), a substrate having a base film is provided, and in control (b), a metal-containing resist film is formed on the base film, and control (b) includes: control (b1), forming a first resist film containing metal on the base film; and control (b2), forming a second resist film containing metal at a composition ratio different from that of the first resist film on the first resist film.

[0047] In an exemplary embodiment, a substrate processing system is provided, comprising one or more substrate processing devices and a control unit, wherein the control unit is configured to enable the one or more substrate processing devices to perform: control (a) to provide a substrate, wherein the substrate has a base film and a metal-containing resist film on the base film, the metal-containing resist film comprising a first resist film containing metal on the base layer, and a second resist film containing metal on the first resist film at a composition ratio different from that of the first resist film, the metal-containing resist film comprising an exposed first area and an unexposed second area; and control (b) to develop the substrate to selectively remove the second area from the metal-containing resist film.

[0048] Hereinafter, various embodiments of the present invention will be described in detail with reference to the accompanying drawings. In addition, the same reference numerals are used for the same or identical elements in the various drawings, and repeated descriptions are omitted. Unless otherwise specified, the positional relationships such as up, down, left, and right are described based on the positional relationships shown in the drawings. The dimensional ratios in the drawings do not represent the actual ratios, and the actual ratios are not limited to the ratios shown in the drawings.

[0049] <Configuration example of heat treatment system>

[0050] Figure 1 1 is a diagram for explaining a configuration example of a heat treatment system. In one embodiment, the heat treatment system includes a heat treatment apparatus 100 and a control unit 200. The heat treatment system is an example of a substrate processing system, and the heat treatment apparatus 100 is an example of a substrate processing apparatus.

[0051] The heat treatment device 100 has a processing chamber 102 configured to form a closed space. The processing chamber 102 is, for example, an airtight cylindrical container configured to adjust the atmosphere inside. A side wall heater 104 is provided on the side wall of the processing chamber 102. A ceiling heater 130 is provided on the ceiling wall (ceiling) of the processing chamber 102. The ceiling surface 140 of the ceiling wall (ceiling) of the processing chamber 102 is formed as a horizontal flat surface, and its temperature can be adjusted by the ceiling heater 130.

[0052] A substrate support portion 121 is provided on the lower side of the processing chamber 102. The substrate support portion 121 has a substrate support surface on which a substrate W can be supported. The substrate support portion 121 is formed, for example, to be circular when viewed from above, and a substrate W can be placed on its surface (upper surface) formed horizontally. A stage heater 120 is embedded in the substrate support portion 121. The stage heater 120 can heat the substrate W placed on the substrate support portion 121. In addition, a ring assembly (not shown) can be arranged in the substrate support portion 121 in a manner to surround the substrate W. The ring assembly can include one or more annular components. By arranging the ring assembly around the substrate W, the temperature controllability of the peripheral area of ​​the substrate W can be improved. The ring assembly can be composed of an inorganic material or an organic material according to the target heat treatment.

[0053] The substrate support portion 121 is supported in the processing chamber 102 by a support 122 provided on the bottom surface of the processing chamber 102. A plurality of pins 123 capable of vertical lifting and lowering are provided on the circumferential outer side of the support 122. The plurality of lifting pins 123 are respectively inserted into through holes provided in the substrate support portion 121. The plurality of lifting pins 123 are arranged at intervals in the circumferential direction. The lifting and lowering movement of the plurality of lifting pins 123 is controlled by a lifting mechanism 124. When the lifting pins 123 extend from the surface of the substrate support portion 121, the substrate W can be transferred between the conveying mechanism (not shown) and the substrate support portion 121.

[0054] An exhaust port 131 having an opening is provided on the side wall of the processing chamber 102. The exhaust port 131 is connected to an exhaust mechanism 132 via an exhaust pipe. The exhaust mechanism 132 is composed of a vacuum pump and a valve, etc., and adjusts the exhaust flow rate from the exhaust port 131. By adjusting the exhaust flow rate and the like using the exhaust mechanism 132, the pressure in the processing chamber 102 can be adjusted. In addition, a conveying port for a substrate W (not shown) is formed on the side wall of the processing chamber 102 in an openable and closable manner at a position different from the opening position of the exhaust port 131.

[0055] In addition, a gas nozzle 141 is provided on the side wall of the processing chamber 102 at a position different from the exhaust port 131 and the transfer port of the substrate W. The gas nozzle 141 supplies the processing gas into the processing chamber 102. The gas nozzle 141 is provided on the side wall of the processing chamber 102 on the opposite side of the exhaust port 131 when viewed from the center of the substrate support portion 121. That is, the gas nozzle 141 is provided on the side wall of the processing chamber 102 symmetrically with the exhaust port 131 with respect to the vertical virtual plane passing through the center of the substrate support portion 121.

[0056] The gas nozzle 141 is formed in a rod shape extending from the side wall of the processing chamber 102 toward the center of the processing chamber 102. The front end of the gas nozzle 141 extends horizontally from the side wall of the processing chamber 102. The processing gas is ejected into the processing chamber 102 from the ejection port opened at the front end of the gas nozzle 141. Figure 1 The gas flows in the direction of the dashed arrow shown and is exhausted from the exhaust port 131. In addition, the front end of the gas nozzle 41 may have a shape extending obliquely downward toward the substrate W, or may have a shape extending obliquely upward toward the ceiling surface 140 of the processing chamber 102.

[0057] In addition, the gas nozzle 141 may be disposed on, for example, a ceiling wall of the processing chamber 102. The exhaust port 131 may be disposed on a bottom surface of the processing chamber 102.

[0058] The heat treatment apparatus 100 has a gas supply pipe 152 connected to the gas nozzle 141 from the outside of the processing chamber 102. A pipe heater 160 for heating the gas in the gas supply pipe is provided around the gas supply pipe 152. The gas supply pipe 152 is connected to a gas supply unit 170. The gas supply unit 170 includes at least one gas source and at least one flow controller. The gas supply unit may include a vaporizer that vaporizes a material in a liquid state.

[0059] The control unit 200 can process computer executable commands, which are used to make the heat treatment device 100 perform various processes described in the present invention. The control unit 200 can be configured to control the various elements of the heat treatment device 100 to perform various processes described herein. In one embodiment, a part or all of the control unit 200 can be included in the heat treatment device 100. The control unit 200 can include a processing unit 200a1, a storage unit 200a2 and a communication interface 200a3. The control unit 200 is implemented, for example, by a computer 200a. The processing unit 200a1 can be configured to read a program from the storage unit 200a2 and perform various control actions by executing the read program. The program can be stored in the storage unit 200a2 in advance, or it can be obtained via a medium when necessary. The obtained program is stored in the storage unit 200a2, and is read and executed from the storage unit 200a2 by the processing unit 200a1. The medium can be various storage media that can be read by the computer 200a, or it can be a communication line connected to the communication interface 200a3. The processing unit 200a1 may be a CPU (Central Processing Unit). The storage unit 200a2 may include a RAM (Random Access Memory), a ROM (Read Only Memory), a HDD (Hard Disk Drive), an SSD (Solid State Drive), or a combination thereof. The communication interface 200a3 may communicate with the heat treatment device 100 via a communication line such as a LAN (Local Area Network).

[0060] <Configuration example of plasma processing system>

[0061] Figure 2 : is a diagram for illustrating a structural example of a plasma processing system. In one embodiment, the plasma processing system includes a plasma processing device 1 and a control unit 2. The plasma processing system is an example of a substrate processing system, and the plasma processing device 1 is an example of a substrate processing device. The plasma processing device 1 includes a plasma processing chamber (hereinafter referred to as a "processing chamber") 10, a substrate support portion 11, and a plasma generating portion 12. The plasma processing chamber 10 has a plasma processing space. In addition, the plasma processing chamber 10 has at least one gas supply port for supplying at least one processing gas to the plasma processing space, and at least one gas exhaust port for exhausting gas from the plasma processing space. The gas supply port is connected to the gas supply portion 20 described later, and the gas exhaust port is connected to the exhaust system 40 described later. The substrate support portion 11 is arranged in the plasma processing space and has a substrate supporting surface for supporting a substrate.

[0062] The plasma generating unit 12 is configured to generate plasma from at least one processing gas supplied to the plasma processing space. The plasma formed in the plasma processing space is a capacitively coupled plasma (CCP: Capacitively Coupled Plasma), an inductively coupled plasma (ICP: Inductively Coupled Plasma), an ECR plasma (Electron-Cyclotron-resonance plasma), a helicon wave excited plasma (HWP: Helicon Wave Plasma) or a surface wave plasma (SWP: Surface Wave Plasma), etc. In addition, various types of plasma generating units including an AC (Alternating Current) plasma generating unit and a DC (Direct Current) plasma generating unit can be used. In one embodiment, the AC signal (AC power) used in the AC plasma generating unit has a frequency in the range of 100kHz to 10GHz. Therefore, the AC signal includes an RF (Radio Frequency) signal and a microwave signal. In one embodiment, the RF signal has a frequency in the range of 100kHz to 150MHz.

[0063] The control unit 2 can process computer-executable commands for causing the plasma processing apparatus 1 to execute the various processes described in the present invention. The control unit 2 can be configured to control the various elements of the plasma processing apparatus 1 to execute the various processes described herein. In one embodiment, a portion or all of the control unit 2 can be included in the plasma processing apparatus 1. The control unit 2 is implemented, for example, by a computer 2a. The control unit 2 can include a processing unit 2a1, a storage unit 2a2, and a communication interface 2a3. The various structures of the control unit 2 can be connected to the control unit 200 described above (see Figure 1 ) have the same structures.

[0064] Hereinafter, a configuration example of a capacitive coupling type plasma processing apparatus will be described as an example of the plasma processing apparatus 1 . Figure 3 It is a diagram for explaining a configuration example of a capacitive coupling type plasma processing apparatus.

[0065] A capacitively coupled plasma processing apparatus 1 includes a plasma processing chamber 10, a gas supply unit 20, a power supply 30, and an exhaust system 40. In addition, the plasma processing apparatus 1 includes a substrate support unit 11 and a gas introduction unit. The gas introduction unit is configured to be able to introduce at least one processing gas into the plasma processing chamber 10. The gas introduction unit includes a shower head 13. The substrate support unit 11 is disposed in the plasma processing chamber 10. The shower head 13 is disposed above the substrate support unit 11. In one embodiment, the shower head 13 constitutes at least a portion of the ceiling of the plasma processing chamber 10. The plasma processing chamber 10 has a plasma processing space 10s defined by the shower head 13, the side wall 10a of the plasma processing chamber 10, and the substrate support unit 11. The plasma processing chamber 10 is grounded. The shower head 13 and the substrate support unit 11 are electrically insulated from the shell of the plasma processing chamber 10.

[0066] The substrate support portion 11 includes a main body 111 and a ring assembly 112. The main body 111 has a central area 111a for supporting a substrate W and an annular area 111b for supporting the ring assembly 112. A wafer is an example of a substrate W. The annular area 111b of the main body 111 surrounds the central area 111a of the main body 111 when viewed from above. The substrate W is arranged on the central area 111a of the main body 111, and the ring assembly 112 is arranged on the annular area 111b of the main body 111 in a manner of surrounding the substrate W on the central area 111a of the main body 111. Therefore, the central area 111a is also referred to as a substrate support surface for supporting the substrate W, and the annular area 111b is also referred to as a ring support surface for supporting the ring assembly 112.

[0067] In one embodiment, the main body 111 includes a base 1110 and an electrostatic chuck 1111. The base 1110 includes a conductive component. The conductive component of the base 1110 can function as a lower electrode. The electrostatic chuck 1111 is arranged on the base 1110. The electrostatic chuck 1111 includes a ceramic component 1111a and an electrostatic electrode 1111b arranged in the ceramic component 1111a. The ceramic component 1111a has a central area 111a. In one embodiment, the ceramic component 1111a also has an annular area 111b. In addition, the annular area 111b may also be provided by other components surrounding the electrostatic chuck 1111, such as an annular electrostatic chuck and an annular insulating component. In this case, the ring assembly 112 may be arranged on the annular electrostatic chuck or the annular insulating component, or on both the electrostatic chuck 1111 and the annular insulating component. In addition, at least one RF / DC electrode coupled to the RF power supply 31 and / or DC power supply 32 described later may be arranged in the ceramic component 1111a. In this case, at least one RF / DC electrode functions as a lower electrode. In the case where the bias RF signal and / or DC signal described later is supplied to at least one RF / DC electrode, the RF / DC electrode is also referred to as a bias electrode. In addition, the conductive component of the base 1110 and at least one RF / DC electrode may function as a plurality of lower electrodes. In addition, the electrostatic electrode 1111b may function as a lower electrode. Therefore, the substrate support portion 11 includes at least one lower electrode.

[0068] The ring assembly 112 includes one or more ring-shaped components. In one embodiment, the one or more ring-shaped components include one or more edge rings and at least one cover ring. The edge ring is formed of a conductive material or an insulating material, and the cover ring is formed of an insulating material.

[0069] In addition, the substrate support portion 11 may include a temperature adjustment module, which is configured to adjust at least one of the electrostatic chuck 1111, the ring assembly 112 and the substrate to a target temperature. The temperature adjustment module may include a heater, a heat transfer medium, a flow path 1110a or a combination thereof. A heat transfer fluid such as brine or gas flows in the flow path 1110a. In one embodiment, the flow path 1110a is formed in the base 1110, and one or more heaters are arranged in the ceramic part 1111a of the electrostatic chuck 1111. In addition, the substrate support portion 11 may include a heat transfer gas supply portion, which is configured to supply a heat transfer gas to the gap between the back side of the substrate W and the central area 111a.

[0070] The showerhead 13 is configured to be able to introduce at least one processing gas from the gas supply unit 20 into the plasma processing space 10s. The showerhead 13 has at least one gas supply port 13a, at least one gas diffusion chamber 13b, and a plurality of gas introduction ports 13c. The processing gas supplied to the gas supply port 13a is introduced into the plasma processing space 10s from the plurality of gas introduction ports 13c through the gas diffusion chamber 13b. In addition, the showerhead 13 includes at least one upper electrode. In addition, in addition to the showerhead 13, the gas introduction unit may also include one or more side gas injection units (SGI: Side Gas Injector) installed at one or more openings formed in the side wall 10a.

[0071] The gas supply unit 20 may include at least one gas source 21 and at least one flow controller 22. In one embodiment, the gas supply unit 20 is configured to supply at least one process gas from the respectively corresponding gas source 21 to the nozzle 13 via the respectively corresponding flow controller 22. Each flow controller 22 may include, for example, a mass flow controller or a pressure-controlled flow controller. Furthermore, the gas supply unit 20 may include at least one flow modulation device for modulating or pulsing the flow of at least one process gas.

[0072] The power supply 30 includes an RF power supply 31 coupled to the plasma processing chamber 10 via at least one impedance matching circuit. The RF power supply 31 is configured to supply at least one RF signal (RF power) to at least one lower electrode and / or at least one upper electrode. Thus, plasma can be formed from at least one processing gas supplied to the plasma processing space 10s. Therefore, the RF power supply 31 can function as at least a part of the plasma generating unit 12, and in addition, by supplying a bias RF signal to at least one lower electrode, a bias potential can be generated on the substrate W, and ion components in the formed plasma can be attracted to the substrate W.

[0073] In one embodiment, the RF power supply 31 includes a first RF generator 31a and a second RF generator 31b. The first RF generator 31a is configured to couple with at least one lower electrode and / or at least one upper electrode via at least one impedance matching circuit to generate a generation source RF signal (generation source RF power) for plasma generation. In one embodiment, the generation source RF signal has a frequency in the range of 10 MHz to 150 MHz. In one embodiment, the first RF generator 31a can be configured to generate a plurality of generation source RF signals having different frequencies. The generated one or more generation source RF signals are supplied to at least one lower electrode and / or at least one upper electrode.

[0074] The second RF generating unit 31b is configured to couple with at least one lower electrode via at least one impedance matching circuit to generate a bias RF signal (bias RF power). The frequency of the bias RF signal may be the same as or different from the frequency of the generating source RF signal. In one embodiment, the bias RF signal has a frequency lower than the frequency of the generating source RF signal. In one embodiment, the bias RF signal has a frequency in the range of 100 kHz to 60 MHz. In one embodiment, the second RF generating unit 31b may be configured to generate a plurality of bias RF signals having different frequencies. The generated one or more bias RF signals are supplied to at least one lower electrode. In addition, in various embodiments, at least one of the generating source RF signal and the bias RF signal may be pulsed.

[0075] In addition, the power supply 30 may include a DC power supply 32 coupled to the plasma processing chamber 10. The DC power supply 32 includes a first DC generating unit 32a and a second DC generating unit 32b. In one embodiment, the first DC generating unit 32a is configured to be connected to at least one lower electrode to generate a first DC signal. The generated first DC signal is applied to at least one lower electrode. In one embodiment, the second DC generating unit 32b is configured to be connected to at least one upper electrode to generate a second DC signal. The generated second DC signal is applied to at least one upper electrode.

[0076] In various embodiments, the first and second DC signals may be pulsed. In this case, a sequence of voltage pulses is applied to at least one lower electrode and / or at least one upper electrode. The voltage pulse may have a pulse waveform of a rectangle, a trapezoid, a triangle, or a combination thereof. In one embodiment, a waveform generator for generating a sequence of voltage pulses from a DC signal is connected between the first DC generator 32a and at least one lower electrode. Therefore, the first DC generator 32a and the waveform generator constitute a voltage pulse generator. In the case where the voltage pulse generator is constituted by the second DC generator 32b and the waveform generator, the voltage pulse generator is connected to at least one upper electrode. The voltage pulse may have a positive polarity or a negative polarity. In addition, the sequence of voltage pulses may include one or more positive polarity voltage pulses and one or more negative polarity voltage pulses in one cycle. In addition, the first and second DC generators 32a, 32b may be provided together with the RF power supply 31, or the first DC generator 32a may be provided instead of the second RF generator 31b.

[0077] The exhaust system 40 can be connected to the gas exhaust port 10e provided at the bottom of the plasma processing chamber 10, for example. The exhaust system 40 can include a pressure regulating valve and a vacuum pump. The pressure in the plasma processing space 10s can be adjusted by the pressure regulating valve. The vacuum pump can include a turbomolecular pump, a dry pump, or a combination thereof.

[0078] <Configuration example of liquid handling system>

[0079] Figure 4 3 is a diagram for explaining a configuration example of a liquid processing system. In one embodiment, the liquid processing system includes a liquid processing apparatus 300 and a control unit 400. The liquid processing system is an example of a substrate processing system, and the liquid processing apparatus 300 is an example of a substrate processing apparatus.

[0080] like Figure 4 As shown, the liquid processing apparatus 300 has a spin chuck 311 as a substrate support portion in a processing chamber 310. The spin chuck 311 holds the substrate W horizontally. The spin chuck 311 is connected to a lifting and lowering rotating portion 312, and the rotating portion 312 is connected to a rotation driving portion 313 composed of a motor or the like. The substrate W held on the spin chuck 311 can be rotated by the driving of the rotation driving portion 313.

[0081] A cup-shaped portion 321 is disposed outside the spin chuck 311 to prevent the processing liquid (resist liquid, developer, cleaning liquid, etc.) and the spray of the processing liquid from scattering around the cup-shaped portion 321. A drain pipe 323 and an exhaust pipe 324 are provided at the bottom 322 of the cup-shaped portion 321. The drain pipe 323 is connected to a drain device 325 such as a drain pump. The exhaust pipe 324 is connected to an exhaust device 327 such as an exhaust pump via a valve 326.

[0082] Air supply device 314 is provided above processing chamber 310 of liquid processing apparatus 300 , and air supply device 314 supplies air of a required temperature and humidity toward cup-shaped portion 321 in the form of downward airflow.

[0083] When a liquid film (puddle) of the processing liquid is formed on the substrate W, a processing liquid supply nozzle 331 is used. The processing liquid supply nozzle 331 is provided on a nozzle support portion 332 such as a support arm, and the nozzle support portion 332 can be raised and lowered as shown by the dotted line reciprocating arrow A in the figure, and can be moved horizontally as shown by the dotted line reciprocating arrow B under the action of a driving mechanism. The processing liquid (resist liquid, developer, etc.) is supplied from the processing liquid supply source 334 to the processing liquid supply nozzle 331 via a supply pipe 333.

[0084] When forming a liquid film, when using a so-called elongated nozzle having a discharge port having a length greater than the diameter of the substrate W, a liquid film of the treatment liquid can be formed on the substrate W by scanning from one end to the other end on the substrate W. In addition, when using a so-called straight-type nozzle that discharges liquid in a manner of forming a liquid column having a width sufficiently small relative to the diameter of the substrate W, the discharge port is located above the center of the substrate W, and the treatment liquid is discharged while the substrate W is rotated, thereby allowing the treatment liquid to spread over the entire surface of the substrate W, thereby forming a liquid film of the treatment liquid on the substrate W. In addition, the liquid film of the treatment liquid can also be formed by scanning the vertical-type nozzle on the substrate W in the same manner as the elongated nozzle, or by arranging a plurality of discharge ports that discharge liquid like the vertical-type nozzle on the substrate W, and supplying the treatment liquid from each discharge port.

[0085] The gas nozzle 341 has a nozzle body 342. The nozzle body 342 is provided on a nozzle support such as a support arm, and the nozzle support can be raised and lowered as indicated by a reciprocating arrow C shown by a dotted line in the figure, and can be moved horizontally as indicated by a reciprocating arrow D shown by a dotted line, by a driving mechanism.

[0086] The gas nozzle 341 has two nozzle outlets 343 and 344. The nozzle outlets 343 and 344 are formed by branching from a gas flow path 345. The gas flow path 345 is connected to a gas supply source 347 via a gas supply pipe 346. In the gas supply source 347, nitrogen gas, for example, is prepared as an inert gas or a non-oxidizing gas. When nitrogen gas, for example, is supplied from the gas flow path 345 to the gas nozzle 341, nitrogen gas is ejected from each nozzle outlet 343 and 344.

[0087] In addition, the gas nozzle 341 is provided with a cleaning liquid supply nozzle 351 for cleaning the processing liquid after liquid treatment from the substrate W. The cleaning liquid supply nozzle 351 is connected to the cleaning liquid supply source 353 via a cleaning liquid supply pipe 352. As the cleaning liquid, pure water is used, for example. The cleaning liquid supply nozzle 351 is located between the above-mentioned two nozzle outlets 343 and 344, but its position is not limited to this. The cleaning liquid supply nozzle 351 can also be a structure independent of the gas nozzle 341.

[0088] The control unit 400 can process computer-executable commands for causing the liquid processing device 300 to perform the various processes described in the present invention. The control unit 400 can be configured to control the various elements of the liquid processing device 300 to perform the various processes described herein. In one embodiment, a portion or all of the control unit 400 can be included in the liquid processing device 300. The control unit 400 can be implemented, for example, by a computer 400a. The computer 400a may include a processing unit 400a1, a storage unit 400a2, and a communication interface 400a3. The various structures of the control unit 400 can be connected to the control unit 200 described above (see Figure 1 ) have the same structures.

[0089] <An example of substrate processing method>

[0090] Figure 5 It is a flowchart representing a substrate processing method (hereinafter also referred to as "the present processing method") according to an exemplary embodiment. The present processing method includes: a process ST1 of providing a substrate having a base film; and a process ST2 of forming a metal-containing resist film on the base film. In one embodiment, the formation process of the metal-containing resist film in process ST2 (hereinafter also referred to as "film forming process") is performed by a dry process using a processing gas (hereinafter also referred to as "dry film forming"). In one embodiment, the film forming process in process ST2 is performed by a wet process using a solution (hereinafter also referred to as "wet film forming"). In one embodiment, the film forming process in process ST2 is performed by wet film forming, and the film forming process in process ST3 is performed by dry film forming. In one embodiment, the film forming process in process ST2 is performed using both wet film forming and dry film forming.

[0091] This processing method can use the above-mentioned substrate processing system (refer to Figure 1~Figure 4 ) can be performed by any one of the substrate processing systems. In addition, two or more of these substrate processing systems can also be used to perform the process. For example, the processing method can be performed by a heat treatment system (refer to Figure 1 In the following description, the case where the control unit 200 controls each part of the heat treatment apparatus 100 to perform the processing method on the substrate W is described as an example.

[0092] (Step ST1: Providing a substrate)

[0093] First, in step ST1, a substrate W is provided to the processing chamber 102 of the heat treatment device 100. The substrate W is provided to the substrate support part 121 via the lifting pins 123. After the substrate W is arranged on the substrate support part 121, the temperature of the substrate support part 121 is adjusted to a set temperature. The set temperature can be, for example, a temperature below 300°C, or a temperature above 100°C and below 300°C. The temperature adjustment of the substrate support part 121 can be performed by controlling the output of one or more heaters among the side wall heater 104, the mounting table heater 120, the ceiling heater 130 and the pipe heater 160 (hereinafter also collectively referred to as "each heater"). In this processing method, the temperature of the substrate support part 121 can be adjusted to the set temperature before step ST1. That is, the substrate W can be provided to the substrate support part 121 after the temperature of the substrate support part 121 is adjusted to the set temperature.

[0094] The substrate W can be used to manufacture semiconductor devices. The semiconductor devices include, for example, memory devices such as DRAM and 3D-NAND flash memory and logic devices. The substrate W has a base film UF. The base film UF can be an organic film, a dielectric film, a metal film or a semiconductor film or a laminated film thereof formed on a silicon wafer. In one embodiment, the base film UF includes, for example, at least one selected from a silicon-containing film, a carbon-containing film and a metal-containing film.

[0095] Figure 6 and Figure 7 They are diagrams showing an example of a base film UF of a substrate W. Figure 6 As shown, the base film UF can be composed of a first film UF1, a second film UF2 and a third film UF3. Figure 7 As shown, the base film UF may also be composed of a second film UF2 and a third film UF3. In one embodiment, the surface of the base film UF may be subjected to a water-repellent treatment for improving adhesion with the metal-containing film.

[0096] The first film UF1 is, for example, a spin-on glass (SOG) film, a SiC film, a SiON film, a Si-containing anti-reflection film (SiARC), or an organic film. The second film UF2 is, for example, a spin-on carbon (SOC) film, an amorphous carbon film, or a silicon-containing film. The third film UF3 is, for example, a silicon-containing film. The silicon-containing film is, for example, a silicon oxide film, a silicon nitride film, a silicon oxynitride film, a silicon carbon nitride film, a polycrystalline silicon film, or a carbon-containing silicon film. The third film UF3 can be composed of a plurality of stacked silicon-containing films. For example, the third film UF3 can be composed of alternately stacked silicon oxide films and silicon nitride films. In addition, the third film UF3 can be composed of stacked silicon oxide films and polycrystalline silicon films. In addition, the third film UF3 can also be a stacked film including a silicon nitride film, a silicon oxide film, and a polycrystalline silicon film. In addition, the third film UF3 can also be composed of a stacked silicon oxide film and a silicon carbon nitride film. In addition, the third film UF3 may be a stacked film including a silicon oxide film, a silicon nitride film, and a silicon carbonitride film.

[0097] A part or all of the base film UF may be formed in the processing chamber 102 of the heat treatment apparatus 100. In addition, other systems, such as a plasma processing system (see Figure 2 and Figure 3 )、Liquid handling system (refer to Figure 4 ) to form.

[0098] (Step ST2: Forming a Metal-Containing Resist Film)

[0099] Next, in step ST2, a metal-containing resist film RM is formed on the base film UF of the substrate W. In one embodiment, step ST2 includes a step ST21 of forming a first resist film RM1 and a step ST22 of forming a second resist film RM2.

[0100] (Step ST21: Forming a First Resist Film)

[0101] In step ST21 , a first resist film RM1 is formed. Figure 8 FIG. 1 is a diagram showing an example of a cross-sectional structure of a substrate W on which a first resist film RM1 is formed in step ST21. Figure 8 As shown, the first resist film RM1 is formed on the surface of the base film UF. The first resist film RM1 is a film containing a metal. In one embodiment, the first resist film RM1 contains at least one metal selected from Sn, Hf and Ti. In one example, the first resist film RM1 may contain Sn.

[0102] The first resist film RM1 in step ST21 can be formed by various methods such as atomic layer deposition (ALD), chemical vapor deposition (CVD), etc. An example of various methods for forming the first resist film RM1 will be described below.

[0103] [ALD method]

[0104] In one embodiment, the first resist film RM1 is formed by allowing a predetermined material to be autonomously adsorbed and reacted on the base film UF of the substrate W by the ALD method.

[0105] Fig. 9 1 is a flowchart showing an example of step ST21 using the ALD method. Fig. 9 As shown, the process ST21 using the ALD method includes a process ST211 of forming a metal-containing precursor film, a first purge process ST212, a process ST213 of forming a metal-containing film from the metal-containing precursor film, a second purge process ST214, and a determination process ST215. Among them, the first purge process ST212 and the second purge process ST214 may or may not be performed. In addition, Fig.10 This is a diagram schematically showing an example of a phenomenon occurring on the surface of the substrate W in the step ST21 using the ALD method.

[0106] In step ST211, if Fig.10As shown, a first gas G1 containing a metal-containing precursor is supplied to the surface of the base film UF to form a metal-containing precursor film PF. In one embodiment, the metal-containing precursor is a metal-containing organic precursor. In one embodiment, the metal-containing precursor contains at least one metal selected from Sn, Hf and Ti. For example, the metal-containing precursor contains at least one compound selected from tin alkane compounds, oxygen-containing tin compounds, nitrogen-containing tin compounds and tin halide compounds. Examples of tin alkane compounds can include tin alkane, tetramethyltin alkane, tributyltin alkane, phenyltrimethyltin alkane, tetravinyltin alkane, dimethyldichlorotin alkane, butyltrichlorotin alkane, trichlorophenyltin alkane, etc. Examples of oxygen-containing tin compounds can include tributyltin methoxide, tert-butoxytin, dibutyltin diacetate, triphenyltin acetate, tributyltin oxide, triphenyltin acetate, triphenyltin hydroxide, butylchlorotin dihydroxide (Butylchlorotin dihydroxide), tin acetylacetonate, etc. Examples of nitrogen-containing tin compounds can include dimethylaminotrimethyltin, tris(dimethylamino)tert-butyltin, trimethyltin azide, tetrakis(dimethylamino)tin, N,N'-di-tert-butyl-2,3-diamidobutanetin(II), etc. Examples of tin halide compounds can include tin chloride, tin bromide, tin iodide, dimethyltin dichloride, butyltin trichloride, phenyltin trichloride, etc.

[0107] In step ST211 of one embodiment, the first gas G1 is supplied into the processing chamber 102 via the gas nozzle 141. Then, in the chamber 102, the metal-containing precursor of the first gas G1 is adsorbed on the surface of the base film UF to form the metal-containing precursor film PF. The metal-containing precursor film PF can contain Sn, Hf, Ti, etc. The metal-containing precursor film PF can be a metal complex. The metal complex can contain aminotin, for example.

[0108] In step ST212, the gas in the chamber 102 is exhausted from the exhaust port 131 by the exhaust mechanism 132. At this time, an inert gas or the like may be supplied to the substrate W. Thus, the excess gas containing the metal precursor or the like is purged. In one example, the inert gas is a rare gas such as He, Ar, Ne, Kr, Xe, or nitrogen.

[0109] In step ST213, if Fig.10As shown, a second gas G2 containing an oxidizing gas is supplied to the surface of the substrate W, and the second gas G2 reacts with the metal-containing precursor film PF to form a metal-containing film from the metal-containing precursor film PF. The oxidizing gas contained in the second gas G2 is a gas that can react with the metal-containing precursor adsorbed on the surface of the base film UF. The oxidizing gas can be at least one selected from H2O gas, H2O2 gas, O3 gas and O2 gas. In step ST213 of one embodiment, the second gas G2 is supplied to the processing chamber 102 via the gas nozzle 141. Then, in the chamber 102, the second gas G2 reacts with the metal-containing precursor film PF to form a metal-containing film.

[0110] In step ST214, the gas in the chamber 102 is exhausted from the exhaust port 131 by the exhaust mechanism 132. At this time, an inert gas or the like may be supplied to the substrate W. Thereby, an excessive gas such as the second gas G2 is purged.

[0111] In process ST215, it is determined whether the prescribed conditions for ending process ST21 have been satisfied. The prescribed conditions may be that the process of process ST211 to process ST214 as one cycle has been performed a predetermined number of times. The number of times may be 1 time, less than 5 times, more than 5 times, or more than 10 times. If it is determined in process ST215 that the prescribed conditions are not satisfied, the process returns to process ST211, and if it is determined that the prescribed conditions are satisfied, process ST21 ends. For example, the prescribed conditions may also be conditions on the size of the metal-containing film after process ST214. That is, after process ST214, it is determined whether the size of the metal-containing film (the thickness of the resist film) has reached a prescribed value or range, and the cycle of process ST211 to process ST214 may be repeated until the prescribed value or range is reached. The size of the first resist film RM1 may be measured by an optical measuring device. In the above manner, the first resist film RM1 can be formed on the base film UF.

[0112] [CVD method]

[0113] In one embodiment, the first resist film RM1 is formed by a CVD method using a mixed gas GM containing a metal-containing gas and an oxidizing gas. The metal-containing gas may contain the metal-containing precursor described in the ALD method. The oxidizing gas may be at least one selected from H2O gas, H2O2 gas, O3 gas, and O2 gas. In one embodiment, the mixed gas GM is supplied to the processing chamber 102 via a gas nozzle 141. The mixed gas GM chemically reacts on the substrate W, thereby forming a first resist film RM1 on the base film UF.

[0114] In step ST21, the temperature of the substrate support 121 may be controlled to a first temperature. The temperature of the substrate support 121 may be adjusted by controlling the output of one or more heaters. The first temperature may be, for example, 0°C to 250°C, or 0°C to 150°C, and in one example, 150°C.

[0115] In one embodiment, step ST21 may include a step of heating and baking the first resist film RM1. Baking may be performed in an air atmosphere or in an inert atmosphere. Baking may be performed by heating the substrate W to a temperature between 50°C and 250°C, between 50°C and 200°C, or between 80°C and 150°C. In one embodiment, each heater of the heat treatment apparatus 100 may function as a heating unit for baking. In one embodiment, baking may also be performed using other heat treatment systems other than the heat treatment apparatus 100.

[0116] (Step ST22: Forming a Second Resist Film)

[0117] In step ST22 , a second resist film RM2 is formed. Fig.11 FIG. 1 is a diagram showing an example of a cross-sectional structure of a substrate W on which a second resist film RM2 is formed in step ST22. Fig.11 As shown, the second resist film RM2 is formed on the first resist film RM1. The second resist film RM2 is a metal-containing film. In one embodiment, the second resist film RM2 contains at least one metal selected from Sn, Hf, and Ti. In one example, the second resist film RM2 may contain Sn.

[0118] In one embodiment, the type of metal contained in the second resist film RM2 is the same as that in the first resist film RM1. In one example, the first resist film RM1 and the second resist film RM2 may both contain Sn. In one embodiment, the type of metal contained in the second resist film RM2 may also be different from that in the first resist film RM1. In one example, the first resist film RM1 may contain at least one metal selected from Sn, Hf, and Ti, and the second resist film RM2 may contain at least one metal selected from Sn, Hf, and Ti that is different from the metal.

[0119] The composition ratio of the metal in the second resist film RM2, that is, the proportion of the metal element in the entire second resist film RM2 (atomic percentage: at%) is different from the composition ratio of the metal in the first resist film RM1. That is, the composition ratio of the metal in the metal-containing resist film RM changes as it goes from the base film UF to the upper part in the thickness direction. In one embodiment, the composition ratio of the metal in the second resist film RM2 is lower than the composition ratio of the first resist film RM1. That is, it may be that the composition ratio of the metal in the metal-containing resist film RM becomes lower as it goes from the base film UF to the upper part in the thickness direction. In one embodiment, the film density of the metal in the second resist film RM2 is lower than the film density of the metal in the first resist film RM1. That is, it may be that the film density of the metal in the metal-containing resist film RM becomes lower as it goes from the base film UF to the upper part in the thickness direction.

[0120] The formation of the second resist film RM2 in step ST22 can be performed using various methods such as ALD method and CVD method. In one embodiment, the formation of the second resist film RM2 in step ST22 can be performed using the same method as the formation of the first resist film RM1 in step ST21. For example, the ALD method can be used in step ST21 and step ST22. For example, the CVD method can also be used in step ST21 and step ST22.

[0121] When the ALD method is used, in step ST22, the same method as that used in step ST21 is used. Fig. 9 The first gas G1 containing the metal precursor and the second gas G2 containing the oxidizing gas are supplied to the substrate W in the same manner as described above.

[0122] In one embodiment, the flow ratio of the first gas G1 to the second gas G2 in step ST22 is different from that in step ST21. In one embodiment, the flow ratio of the first gas G1 to the second gas G2 in step ST22 is lower than that in step ST21. In this case, the composition ratio of the metal in the second resist film RM2 can be lower than that of the first resist film RM1.

[0123] In one embodiment, the total flow rate of the first gas G1 and the second gas G2 in step ST22 is different from the total flow rate in step ST21. In one embodiment, the total flow rate of the first gas G1 and the second gas G2 in step ST22 is less than the total flow rate in step ST21. In this case, the composition ratio of the metal in the second resist film RM2 can be lower than the composition ratio of the first resist film RM1.

[0124] When the CVD method is used, in step ST22, the mixed gas GM including the metal-containing gas and the oxidizing gas is supplied to the substrate W in the same manner as described in step ST21.

[0125] In one embodiment, the flow rate ratio of the flow rate of the metal-containing gas to the total flow rate of the mixed gas GM in the step ST22 is different from the flow rate ratio in the step ST21. In one embodiment, the flow rate ratio of the flow rate of the metal-containing gas to the total flow rate of the mixed gas GM in the step ST22 is smaller than the flow rate ratio in the step ST21. In this case, the composition ratio of the metal in the second resist film RM2 can be lower than the composition ratio of the first resist film RM1.

[0126] In one embodiment, the total flow rate of the mixed gas GM in the step ST22 is different from the total flow rate of the mixed gas GM in the step ST21. In one embodiment, the total flow rate of the mixed gas GM in the step ST22 is less than the total flow rate of the mixed gas GM in the step ST21. In this case, the composition ratio of the metal in the second resist film RM2 can be lower than the composition ratio of the first resist film RM1.

[0127] In step ST22, the temperature of the substrate support 121 can be controlled to a first temperature in the same manner as in step ST21, or can be controlled to a second temperature different from the first temperature. The temperature of the substrate support 121 can be adjusted by controlling the output of one or more of the heaters. In one embodiment, the second temperature is lower than the first temperature. In this case, the composition ratio of the metal in the second resist film RM2 can be lower than the composition ratio of the first resist film RM1. The second temperature can be, for example, above 0°C and below 250°C, or above 0°C and below 150°C, and in one example is 150°C.

[0128] In one embodiment, step ST22 may include a step of heating and baking the second resist film RM2. Baking may be performed in an air atmosphere or in an inert atmosphere. Baking is performed by heating the substrate W to a temperature between 50°C and 250°C, between 50°C and 200°C, or between 80°C and 150°C. In one embodiment, each heater of the heat treatment device 100 may function as a heating unit for baking. In one embodiment, baking may also be performed using other heat treatment systems other than the heat treatment device 100.

[0129] In this processing method, a first resist film RM1 containing metal is formed on the base film UF in step ST21, and on this basis, a second resist film RM2 containing metal in a composition ratio different from that of the first resist film RM1 is formed on the first resist film RM1 in step ST22. That is, the composition ratio of the metal in the metal-containing resist film RM changes along the thickness direction from the base film UF. By changing the composition ratio of the metal, the sensitivity of the metal-containing resist film RM can change along the thickness direction. Thus, according to this processing method, the exposure sensitivity of the resist film can be adjusted.

[0130] The metal-containing resist film RM can be subjected to EUV exposure in subsequent processes. In EUV exposure, due to the probability fluctuation of photon distribution and the shallow depth of focus, a reduction in exposure may occur below the thickness direction of the metal-containing resist film RM (on the side close to the base film UF). In this regard, for example, the composition ratio of the metal in the first resist film RM1 can be made higher than the composition ratio of the metal in the second resist film RM2 to make the sensitivity of the first resist film RM1 higher than the photosensitivity of the second resist film RM2. Thus, it is possible to compensate for the reduction in exposure below the thickness direction of the metal-containing resist film RM during EUV exposure, and suppress the fluctuation of the exposure reaction (curing) in the thickness direction of the metal-containing resist film RM (as a result, the fluctuation of the development tolerance).

[0131] In one embodiment, the metal-containing resist film RM may be composed of more than three layers of films containing metal. For example, the present processing method may also include a process of forming a third resist film RM3 containing metal on the second resist film RM2 after the process ST22 is completed. In this case, the composition ratio of the metal of the third resist film RM3 may be different from that of the first resist film RM1 and the second resist film RM2. In one embodiment, the composition ratio of the metal of the third resist film RM3 is lower than that of the second resist film RM2, and the composition ratio of the metal of the second resist film RM2 is lower than that of the first resist film RM1. That is, it may be that the composition ratio of the metal in the metal-containing resist film RM decreases in a step-like manner (three steps in this case) as it goes from the base film UF to the upper side in the thickness direction. The same is true when the metal-containing resist film RM is composed of more than four layers of films.

[0132] In one embodiment, the composition (type, flow rate, and flow rate ratio) of the processing gas (first gas G1, second gas G2, mixed gas GM) and the film forming conditions such as the temperature of the substrate support 11 can be changed in step ST21. As a result, the composition ratio of the metal can be continuously changed in the thickness direction of the first resist film RM1. In one embodiment, the composition (type, flow rate, and flow rate ratio) of the processing gas (first gas G1, second gas G2, mixed gas GM) and the film forming conditions such as the temperature of the substrate support 11 can also be changed in step ST22. As a result, the composition ratio of the metal can be continuously changed in the thickness direction of the second resist film RM2.

[0133] In one embodiment, the present treatment method can be performed using a plasma treatment system (see Figure 2 and Figure 3 For example, the metal-containing resist film RM can be formed by providing a substrate W on the substrate support portion 11 in the processing chamber 10 of the plasma processing apparatus 1 (step ST1), and supplying a processing gas from the gas supply portion 20 into the processing chamber 10 (step ST2).

[0134] When a plasma processing system is used, the above-mentioned ALD method or CVD method can be used in step ST21 and step ST22. The composition (type, flow rate and flow ratio) of the processing gas (first gas G1, second gas G2, mixed gas GM, etc.) in step ST21 and step ST22 and the temperature of the substrate support part 11 can be changed in the same way as when a thermal treatment system is used. The temperature of the substrate support part 11 can be adjusted by controlling the pressure of the heat transfer gas (such as He) between the temperature adjustment module, the electrostatic chuck 1111 and the back side of the substrate W. In step ST21 and step ST22, plasma may or may not be generated from the processing gas. As with the use of a thermal treatment system (see Figure 1 ) Similarly, step ST21 and / or step ST22 may include a step of heating the substrate W to perform a baking process. The baking process may be performed using a heat treatment system, for example.

[0135] In one embodiment, the present treatment method can also be performed by using a liquid treatment system (see Figure 4 That is, the metal-containing resist film RM can be formed by providing the substrate W to the spin chuck 311 in the processing chamber 310 of the liquid processing device 300 (step ST1), and applying a film-forming solution (resist solution) to the substrate W from the processing liquid supply nozzle 331 (step ST2).

[0136] In the case of using a liquid processing system, in step ST21 and step ST22, the film-forming solution (resist liquid) may contain a metal-containing precursor. In one embodiment, the metal-containing precursor is a metal-containing organic precursor. In one embodiment, the metal-containing precursor contains at least one metal selected from Sn, Hf and Ti. For example, the metal-containing precursor contains at least one compound selected from tin alkane compounds, oxygen-containing tin compounds, nitrogen-containing tin compounds and tin halide compounds. Examples of tin alkane compounds can include tin alkane, tetramethyltin alkane, tributyltin alkane, phenyltrimethyltin alkane, tetravinyltin alkane, dimethyl dichlorotin alkane, butyltrichlorotin alkane, trichlorophenyltin alkane, etc. Examples of oxygen-containing tin compounds can include tributyltin methoxide, tert-butoxytin, dibutyltin diacetate, triphenyltin acetate, tributyltin oxide, triphenyltin acetate, triphenyltin hydroxide, butylchlorotin dihydroxide (Butylchlorotin dihydroxide), tin acetylacetonate, etc. Examples of nitrogen-containing tin compounds can include dimethylaminotrimethyltin, tris(dimethylamino)tert-butyltin, trimethyltin azide, tetrakis(dimethylamino)tin, N,N'-di-tert-butyl-2,3-diamidobutanetin(II), etc. Examples of tin halide compounds can include tin chloride, tin bromide, tin iodide, dimethyltin dichloride, butyltin trichloride, phenyltin trichloride, etc.

[0137] In the case of using a liquid processing system, in one embodiment, the metal composition ratio of the metal-containing precursor contained in the film-forming solution (resist liquid) in step ST22 is different from the composition ratio in step ST21. In one embodiment, the metal composition ratio of the metal-containing precursor contained in the film-forming solution (resist liquid) in step ST22 is lower than the composition ratio in step ST21. In this case, the metal composition ratio in the second resist film RM2 can be lower than the composition ratio of the first resist film RM1.

[0138] In the case of using a liquid treatment system, step ST21 and / or step ST22 may include a step of heating the substrate W to bake after coating the solution on the substrate W. In one embodiment, baking may be performed using, for example, a heat treatment system (see Figure 1 The baking may be performed in an air atmosphere or in an inert atmosphere. The baking may be performed by heating the substrate W to a temperature of 50° C. to 250° C., 50° C. to 200° C., or 80° C. to 150° C.

[0139] In one embodiment, the formation of the metal-containing resist film RM in the present processing method (step ST2) can be performed by using a heat treatment system (see Figure 1 )、Plasma treatment system (refer to Figure 2 and Figure 3) dry process and liquid handling system (refer to Figure 4 ) by a wet process. For example, the first resist film RM1 may be formed by wet film formation in step ST21, and the second resist film RM2 may be formed by dry film formation in step ST22. In addition, for example, the first resist film RM1 may be formed by dry film formation in step ST21, and the second resist film RM2 may be formed by wet film formation in step ST22.

[0140] In one embodiment, the processing method may include the following steps ST3 to ST5 after step ST2.

[0141] (Process ST3: EUV exposure)

[0142] After step ST2, the substrate W is transported to the exposure device, and EUV is irradiated to the metal-containing resist film RM through the exposure mask (photomask). Thus, a substrate W including a base film UF and a metal-containing resist film RM having a first exposed area and a second unexposed area can be formed. The first area is an area corresponding to an opening provided in the exposure mask (photomask). The second area is an area corresponding to a pattern provided in the exposure mask (photomask). EUV has a wavelength in the range of 10 to 20 nm, for example. EUV can have a wavelength in the range of 11 to 14 nm, and in one example has a wavelength of 13.5 nm. The exposed substrate is transported from the exposure device to a heat treatment device under atmosphere management, and undergoes a heat treatment, namely, post-exposure baking (PEB). Additional heat treatment can also be applied to the substrate W after PEB.

[0143] (Step ST4: Development)

[0144] Next, in step ST4, the metal-containing resist film RM of the substrate W is developed to selectively remove the second region. As described above, the metal-containing resist RM of the present processing method can adjust the exposure sensitivity of the metal-containing resist film RM by changing the composition of the metal from the base film UF along the thickness direction. Therefore, when the metal-containing resist RM is developed in step ST4, the fluctuation (deviation) of the development can be suppressed. In addition, the development of the metal-containing resist film RM can be performed by dry development, can be performed by wet development, or can be performed by combining dry development and wet development.

[0145] In the case of dry developing the metal-containing resist film RM, at least one developing gas is supplied into the processing chamber 102 via the gas nozzle 141. In one embodiment, the developing gas may include at least one selected from hydrogen bromide (HBr), hydrogen fluoride (HF), hydrogen chloride (HCl), boron trichloride (BCl3), organic acids (such as carboxylic acids, alcohols), and β-dicarbonyl compounds. The carboxylic acid in the developing gas may include at least one selected from formic acid (HCOOH), acetic acid (CH3COOH), trichloroacetic acid (CCl3COOH), monofluoroacetic acid (CFH2COOH), difluoroacetic acid (CF2FCOOH), trifluoroacetic acid (CF3COOH), chloro-difluoroacetic acid (CClF2COOH), sulfur-containing acetic acid, thioacetic acid (CH3COSH), mercaptoacetic acid (HSCH2COOH), trifluoroacetic anhydride ((CF3CO)2O) and acetic anhydride ((CH3CO)2O). The alcohol in the developing gas may include, for example, perfluoro-tert-butyl alcohol ((CF3)3COH). The β-dicarbonyl compound in the developing gas may be, for example, acetylacetone (CH3C(O)CH2C(O)CH3), trichloroacetylacetone (CCl3C(O)CH2C(O)CH3), hexachloroacetylacetone (CCl3C(O)CH2C(O)CCl3), trifluoroacetylacetone (CF3C(O)CH2C(O)CH3), hexafluoroacetylacetone (HFAc, CF3C(O)CH2C(O)CF3). In step STa, development may be performed by a thermal reaction between the developing gas and the region RD, or by a chemical reaction between chemical species in the plasma generated from the developing gas and the region RD.

[0146] In addition, the metal-containing resist film RM includes a plurality of resist films RM (e.g., a first resist film RM1 and a second resist film RM2) having different compositions. Therefore, in step ST4, the boundary region between the first resist film RM1 and the second resist film RM2 may be cut away in the horizontal direction to produce a depression, etc. Therefore, in step ST4, the metal-containing resist RM can be developed while protecting the side walls of the metal-containing resist RM. For example, in the case of dry development of the metal-containing resist film RM1, a gas having a sidewall protection effect (hereinafter also referred to as a "protective gas") can be added to the above-mentioned developing gas. By adding the protective gas, a passivation layer can be formed on the side walls of the metal-containing resist film RM, and the metal-containing resist film RM can be prevented from being cut away in the horizontal direction.

[0147] As the protective gas, an oxygen-containing gas can be used. In one example, the protective gas can be at least one selected from O2, CO2, CO, COS, SO2 and H2O. When an oxygen-containing gas is added as the protective gas, a layer containing Sn-O bonds can be formed on the side wall of the metal-containing resist film RM, thereby preventing the metal-containing resist film RM from being cut away in the horizontal direction.

[0148] In addition, as a protective gas, a gas containing carbon and / or silicon can be used. As a carbon-containing gas, for example, at least one selected from hydrocarbons, fluorocarbons and hydrofluorocarbons can be used. As a silicon-containing gas, for example, SiCl4 can be used. In addition, aminotin or the like can also be used as a protective gas. By using these protective gases, a protective layer can be formed on the side wall of the metal-containing resist film RM, thereby preventing the metal-containing resist film RM from being cut away in the horizontal direction.

[0149] In one embodiment, step ST4 may include a step of heating the developed metal-containing resist film RM for baking. Baking may be performed in an air atmosphere or in an inert atmosphere. Baking may be performed by heating the substrate W to a temperature of 150° C. to 250° C. In one embodiment, each heater of the heat treatment device 100 may function as a heating unit for baking. In one embodiment, baking may also be performed using other heat treatment systems other than the heat treatment device 100.

[0150] (Step ST5: Etching)

[0151] After step ST4, the base film UF may be etched. The etching process may be performed, for example, by generating plasma from a processing gas in the processing chamber 10 of the plasma processing device 1. In the etching process, the metal-containing resist film RM acts as a mask, and a recess is formed in the base film UF based on the shape of the opening OP. In addition, when the plasma processing device 1 is used for development in step ST4, the etching process may be continuously performed in the same processing chamber 10 as in step ST12, or may be performed in a processing chamber of another plasma processing device.

[0152] <Configuration example of substrate processing system>

[0153] Fig.12 1 is a block diagram for explaining a structural example of a substrate processing system SS according to an exemplary embodiment. The substrate processing system SS includes a first carrier station CS1, a first processing station PS1, a first interface station IS1, an exposure device EX, a second interface station IS2, a second processing station PS2, a second carrier station CS2, and a control unit CT.

[0154] The first carrier station CS1 carries out the delivery and unloading of the first carrier C1 between the first carrier station CS1 and the system outside the substrate processing system SS. The first carrier station CS1 has a loading table including a plurality of first loading plates ST1. On each first loading plate ST1, a first carrier C1 in a state of storing a plurality of substrates W or in an empty state can be loaded. The first carrier C1 has a shell capable of storing a plurality of substrates W inside. In one example, the first carrier C1 is a FOUP (Front Opening Unified Pod).

[0155] In addition, the first carrier station CS1 transports the substrate W between the first carrier C1 and the first processing station PS1. The first carrier station CS1 also includes a first conveying device HD1. The first conveying device HD1 is arranged in the first carrier station CS1 in a manner of being located between the loading table and the first processing station PS1. The first conveying device HD1 transports and transfers the substrate W between the first carrier C1 on each first loading plate ST1 and the second conveying device HD2 of the first processing station PS1. The substrate processing system SS may also include a loading interlock module. The loading interlock module can be arranged between the first carrier station CS1 and the first processing station PS1. The loading interlock module can switch the pressure inside it to atmospheric pressure or vacuum. "Atmospheric pressure" can be the internal pressure of the first conveying device HD1. "Vacuum" can be a pressure lower than atmospheric pressure, for example, a medium vacuum of 0.1Pa~100Pa. The interior of the second conveying device HD2 can be atmospheric pressure or vacuum. The load lock module may, for example, transport the substrate W from the first transport device HD1 under atmospheric pressure to the second transport device HD2 under vacuum, and transport the substrate W from the second transport device HD2 under vacuum to the first transport device HD1 under atmospheric pressure.

[0156] The first processing station PS1 performs various processes on the substrate W. In one embodiment, the first processing station PS1 includes a pre-processing module PM1, a resist film forming module PM2, and a first heat treatment module PM3 (hereinafter also collectively referred to as "first substrate processing module PMa"). In addition, the first processing station PS1 has a second conveying device HD2 for conveying the substrate W. The second conveying device HD2 can convey and transfer the substrate W between two designated first substrate processing modules PMa, and between the first processing station PS1 and the first carrier station CS1 or the first interface station IS1.

[0157] In the pretreatment module PM1, the substrate W is pretreated. In one embodiment, the pretreatment module PM1 includes a temperature adjustment unit for adjusting the temperature of the substrate W, a high-precision temperature adjustment unit for adjusting the temperature of the substrate W with high precision, and a base film forming unit for forming a part or all of the base film on the substrate W. In one embodiment, the pretreatment module PM1 includes a surface modification treatment unit for performing surface modification on the substrate W. Each treatment unit of the pretreatment module PM1 may include a heat treatment device 100 (see Figure 1 )、Plasma processing device 1 (refer to Figure 2 and Figure 3 ) and / or liquid processing device 300 (refer to Figure 4 ) and constituted.

[0158] In the resist film forming module PM2, a resist film is formed on the substrate W. In one embodiment, the resist film forming module PM2 includes a dry coating unit. The dry coating unit forms the resist film on the substrate W using a dry process such as a vapor deposition method. In one example, the dry coating unit includes a CVD device or an ALD device for chemically evaporating a resist film on the substrate W disposed in the chamber, or a PVD device for physically evaporating a resist film. The dry coating unit may also be a heat treatment device 100 (see Figure 1 ) or plasma processing device 1 (refer to Figure 2 and Figure 3 ).

[0159] In one embodiment, the resist film forming module PM2 includes a wet coating unit. The wet coating unit forms a resist film on the substrate W using a wet process such as a liquid phase deposition method. The wet coating unit can be a liquid processing device 300 (see Figure 4 ).

[0160] In one embodiment, examples of the resist film forming module PM2 include both a wet coating unit and a dry coating unit.

[0161] In the first thermal treatment module PM3, the substrate W is thermally treated. In one embodiment, the first thermal treatment module PM3 includes any one or more of a pre-baking (Post Apply Bake: PAB) unit for heating the substrate W on which the resist film is formed, a temperature adjustment unit for adjusting the temperature of the substrate W, and a high-precision temperature adjustment unit for adjusting the temperature of the substrate W with high precision. Each of these units may have one or more thermal treatment devices. In one example, a plurality of thermal treatment devices may be stacked. The thermal treatment device may be, for example, the thermal treatment device 100 (see Figure 1 ). Each heat treatment may be performed at a predetermined temperature using a predetermined gas.

[0162] The first interface station IS1 has a third transport device HD3. The third transport device HD3 transports and delivers the substrate W between the first processing station PS1 and the exposure device EX. The third transport device HD3 can be configured as a housing for storing the substrate W, and the temperature, humidity, pressure, etc. in the housing can be controlled.

[0163] The exposure device EX uses an exposure mask (reticle, photomask) to expose the resist film on the substrate W. The exposure device EX may be, for example, an EUV exposure device having a light source that generates EUV light.

[0164] The second interface station IS2 has a fourth transport device HD4. The fourth transport device HD4 transports and delivers the substrate W between the exposure device EX and the second processing station PS2. The fourth transport device HD4 can be configured to have a housing for storing the substrate W, and the temperature, humidity, pressure, etc. in the housing can be controlled.

[0165] The second processing station PS2 performs various processes on the substrate W. In one embodiment, the second processing station PS2 includes a second thermal processing module PM4, a measurement module PM5, a development module PM6, and a third thermal processing module PM7 (hereinafter collectively referred to as "second substrate processing module PMb"). In addition, the second processing station PS2 has a fifth conveying device HD5 for conveying the substrate W. The fifth conveying device HD5 conveys and transfers the substrate W between two designated second substrate processing modules PMb, and between the second processing station PS2 and the second carrier station CS2 or the second interface station IS2.

[0166] In the second thermal treatment module PM4, the substrate W is thermally treated. In one embodiment, the thermal treatment module PM4 includes any one or more of a post-exposure bake (PEB) unit for heating the exposed substrate W, a temperature adjustment unit for adjusting the temperature of the substrate W, and a high-precision temperature adjustment unit for adjusting the temperature of the substrate W with high precision. Each of these units may have one or more thermal treatment devices. In one example, a plurality of thermal treatment devices may be stacked. The thermal treatment device may be, for example, the thermal treatment device 100 (see Figure 1 ). Each heat treatment can be performed at a predetermined temperature using a predetermined gas.

[0167] In the measurement module PM5, various measurements are performed on the substrate W. In one embodiment, the measurement module PM5 includes a mounting table for mounting the substrate W and a photographing unit including a photographing device, an illumination device, and various sensors (temperature sensor, reflectivity measurement sensor, etc.). The photographing device may be, for example, a CCD camera that photographs the appearance of the substrate W. Alternatively, the photographing device may be a hyperspectral camera that splits light by wavelength and photographs it. The hyperspectral camera is capable of measuring any one or more of the pattern shape, size, film thickness, composition, and film density of the resist film.

[0168] In the developing module PM6, the substrate W is subjected to a developing process. In one embodiment, the developing module PM6 includes a dry developing unit for performing dry developing on the substrate W. The dry developing unit may be, for example, a heat treatment device 100 (see Figure 1 ) or plasma processing device 1 (refer to Figure 2 and Figure 3 In one embodiment, the developing module PM6 includes a wet developing unit for wet developing the substrate W. The wet developing unit may be, for example, a liquid processing device 300 ( Figure 4 In one embodiment, the developing module PM6 includes both a dry developing unit and a wet developing unit.

[0169] In the third heat treatment module PM7, heat treatment is performed on the substrate W. In one embodiment, the third heat treatment module PM7 includes any one or more of a post-bake (PB) unit for heating the developed substrate W, a temperature adjustment unit for adjusting the temperature of the substrate W, and a high-precision temperature adjustment unit for adjusting the temperature of the substrate W with high precision. Each of these units may have one or more heat treatment devices. In one example, a plurality of heat treatment devices may be stacked. The heat treatment device may be, for example, the heat treatment device 100 (see Figure 1 ). Each heat treatment can be performed at a predetermined temperature using a predetermined gas.

[0170] The second carrier station CS2 carries out the transfer of the second carrier C2 between the second carrier station CS2 and a system outside the substrate processing system SS. The structure and function of the second carrier station CS2 may be the same as those of the first carrier station CS1 described above.

[0171] The control unit CT controls each structure of the substrate processing system SS to perform a predetermined process on the substrate W. The control unit CT stores a process recipe that sets the process steps, process conditions, conveying conditions, etc., and controls each structure of the substrate processing system SS according to the process recipe to perform a predetermined process on the substrate W. The control unit CT may also have various control units ( Figure 1~Figure 4The functions of the control unit 200, the control unit 2 and the control unit 400 shown in the figure may be part of or all of the functions.

[0172] <An example of substrate processing method>

[0173] Fig.13 is a flow chart showing a substrate processing method (hereinafter also referred to as "method MT") according to an exemplary embodiment. Fig.13 As shown, method MT includes: step ST100 of pre-treating a substrate; step ST200 of forming a resist film on a substrate; step ST300 of performing a heat treatment (pre-baking: PAB) on the substrate with the resist film formed thereon; step ST400 of performing EUV exposure on the substrate; step ST500 of performing a heat treatment (post-exposure baking: PEB) on the exposed substrate; step ST600 of measuring the substrate; step ST700 of developing the resist film on the substrate; step ST800 of performing a heat treatment (post-baking: PB) on the developed substrate; and step ST900 of etching the substrate. Method MT may not include one or more of the above-mentioned steps. For example, method MT may not include step ST600, and step ST700 may be performed after step ST500.

[0174] Methods MT can use Fig.12 Hereinafter, a case where the control unit CT of the substrate processing system SS controls each part of the substrate processing system SS to execute the method MT on the substrate W will be described as an example.

[0175] (Process ST100: Pretreatment)

[0176] First, the first carrier C1 containing a plurality of substrates W is sent to the first carrier station CS1 of the substrate processing system SS. The first carrier C1 is placed on the first carrier plate ST1. Then, the substrates W in the first carrier C1 are taken out one by one by the first conveying device HD1 and handed over to the second conveying device HD2 of the first processing station PS1. The substrate W is conveyed to the pretreatment module PM1 by the second conveying device HD2. The substrate W is pretreated by the pretreatment module PM1. The pretreatment may, for example, include one or more of the temperature adjustment of the substrate W, the formation of a part or all of the base film of the substrate W, the heating treatment of the substrate W, and the high-precision temperature adjustment of the substrate W. The pretreatment may include the surface modification treatment of the substrate W.

[0177] (Step ST200: Forming a resist film)

[0178] Next, the substrate W is transported by the second transport device HD2 to the resist film forming module PM2. A resist film is formed on the substrate W by the resist film forming module PM2. In one embodiment, the formation of the resist film is performed using a wet process such as a liquid phase deposition method. For example, a resist film is spin-coated on the substrate W using a wet coating unit of the resist film forming module PM2, thereby forming a resist film. In one embodiment, the formation of the resist film on the substrate W is performed using a dry process such as a vapor phase deposition method. For example, a resist film is evaporated on the substrate W using a dry coating unit of the resist film forming module PM2, thereby forming a resist film. The formation of the resist film in step ST200 can be performed using the present processing method (refer to Figure 5 That is, a metal-containing resist film RM having a first resist film RM1 and a second resist film RM2 may be formed on the substrate W.

[0179] In addition, the formation of the resist film on the substrate W may also be performed using both a dry process and a wet process. For example, after a first resist film is formed on the substrate W by a dry process, a second resist film may be formed on the first resist film by a wet process. In this case, the film thickness, material and / or composition of the first resist film and the second resist film may be the same or different.

[0180] (Process ST300: PAB)

[0181] Next, the substrate W is transported to the first thermal treatment module PM3 by the second transport device HD2. The substrate W is subjected to a heat treatment (pre-baking: PAB) by the first thermal treatment module PM3. The pre-baking can be performed in an atmospheric atmosphere or in an inactive atmosphere. In addition, the pre-baking can be performed by heating the substrate W to above 50°C or above 80°C. The heating temperature of the substrate W can be below 250°C, below 200°C, or below 150°C. In one example, the heating temperature of the substrate can be above 50°C and below 250°C. In the case where a resist film is formed by a dry process in step ST200, in one embodiment, the pre-baking can be continuously performed by a dry coating unit that performs step ST200. In one embodiment, after the pre-baking, a process for removing the resist film at the end of the substrate W (Edge Bead Removal: EBR) can be performed.

[0182] (Process ST400: EUV exposure)

[0183] Next, the substrate W is handed over by the second conveying device HD2 to the third conveying device HD3 of the first interface station IS1. Then, the substrate W is conveyed by the third conveying device HD3 to the exposure device EX. The substrate W receives EUV exposure through the exposure mask (photomask) in the exposure device EX. EUV has a wavelength in the range of 10 to 20 nm, for example. EUV can have a wavelength in the range of 11 to 14 nm, and in one example has a wavelength of 13.5 nm. Thus, a first area exposed to EUV and a second area not exposed to EUV are formed on the substrate W corresponding to the pattern of the exposure mask (photomask). In one embodiment, the film thickness of the first area can be smaller than the film thickness of the second area 2.

[0184] (Process ST500: PEB)

[0185] Next, the substrate W is transferred from the fourth conveyor device HD4 of the second interface station IS2 to the fifth conveyor device HD5 of the second processing station PS2. Then, the substrate W is conveyed to the second thermal processing module PM4 by the fifth conveyor device HD5. Then, the substrate W is subjected to a heat treatment (post-exposure baking: PEB) in the second thermal processing module PM4. The post-exposure baking can be performed in an air atmosphere. In addition, the post-exposure baking is performed by heating the substrate W to a temperature of 180° C. to 250° C.

[0186] (Process ST600: Measurement)

[0187] Next, the substrate W is transported to the measurement module PM5 by the fifth transport device HD5. The measurement of the substrate W is performed by the measurement module PM5. The measurement may be an optical measurement or other measurement. In one embodiment, the measurement performed by the measurement module PM5 includes measuring the appearance and / or size of the substrate W using a CCD camera. In one embodiment, the measurement performed by the measurement module PM5 includes measuring any one or more of the pattern shape, size, film thickness, composition, and film density of the resist film (hereinafter also referred to as "pattern shape, etc.") using a hyperspectral camera.

[0188] In one embodiment, the control unit CT determines whether the substrate W has exposure abnormality based on the measured appearance, size and / or pattern shape of the substrate W. In one embodiment, when the control unit CT determines that there is an exposure abnormality, the substrate W may be reworked or discarded instead of developing in step ST700. The rework of the substrate W may be performed by removing the resist on the substrate W and returning to step ST200 to form a resist film. Rework after development may sometimes cause damage to the substrate W. Damage to the substrate W can be avoided or suppressed by reworking before development.

[0189] (Process ST700: Development)

[0190] Next, the substrate W is transported to the developing module PM6 by the fifth transport device HD5. The resist film of the substrate W is developed in the developing module PM6. By performing the development, any one of the first area exposed to EUV and the second area not exposed to EUV can be selectively removed. The development process can be performed by dry development, and can also be performed by wet development. The development process can also be performed by combining dry development and wet development. After or during the development process, one or more desorption processes can be performed. The desorption process includes removing residues (descum) or smoothing the surface (smoothing) of the resist film and the base film UF using an inert gas such as helium or a plasma of the inert gas.

[0191] (Process ST800: PB)

[0192] Next, the substrate W is transported to the third heat treatment module PM7 by the fifth transport device HD5, and a heat treatment (post-baking) is performed. The post-baking can be performed in an atmospheric atmosphere or in a reduced pressure atmosphere containing N2 or O2. In addition, the post-baking can be performed by heating the substrate W to a temperature of 150°C or more and 250°C or less. The post-baking can be performed by the second heat treatment module PM4 instead of the third heat treatment module PM7. In one embodiment, the optical measurement of the substrate W can be performed by the measurement module PM5 after the post-baking. The measurement can be performed in addition to the measurement in the step ST600, or can be performed instead of the measurement in the step ST600. In one embodiment, the control unit CT determines whether the development pattern of the substrate W has abnormalities such as defects, damage, foreign matter adhesion, etc. based on the measured appearance, size and / or pattern shape of the substrate W. In one embodiment, when the control unit CT determines that there is an abnormality, the etching of the step ST900 can be performed instead of reworking or discarding the substrate W. In one embodiment, when the control unit CT determines that there is an abnormality, the opening size of the resist film of the substrate W may be adjusted using a dry coating unit (CVD device, ALD device, etc.).

[0193] (Process ST900: Etching)

[0194] After the step ST800 is executed, the substrate W is transferred from the fifth conveying device HD5 to the sixth conveying device HD6 of the second carrier station CS2, and is conveyed by the sixth conveying device HD6 to the second carrier C2 of the second carrier plate ST2. Thereafter, the second carrier C2 is conveyed to a plasma processing system (not shown). The plasma processing system may be, for example, Figure 2 and Figure 3The plasma processing system shown. In the plasma processing system, the base film UF of the substrate W is etched using the developed resist film as a mask. In the above manner, the method MT ends. In addition, in the case where the resist film is developed using a plasma processing device in step ST700, etching can continue to be performed in the plasma processing chamber of the plasma processing device. In addition, in the case where the second processing station PS2 includes a plasma processing module in addition to the developing module PM6, etching can be performed in the plasma processing module. The above-mentioned desorption process can be performed more than once before or during etching.

[0195] The embodiments of the present invention also include the following aspects.

[0196] (Note 1)

[0197] A substrate processing method, comprising:

[0198] Step (a), providing a substrate having a base film; and

[0199] Step (b), forming a metal-containing resist film on the base film, wherein:

[0200] The step (b) comprises:

[0201] Step (b1), forming a first resist film containing a metal on the base film; and

[0202] The step (b2) is to form a second resist film on the first resist film, the second resist film containing the metal at a composition ratio different from that of the first resist film.

[0203] (Note 2)

[0204] In the substrate processing method according to Supplementary Note 1, a composition ratio of the metal in the second resist film is lower than a composition ratio of the metal in the first resist film.

[0205] (Note 3)

[0206] The substrate processing method according to Supplementary Note 1 or 2, wherein the metal-containing resist film contains at least one metal selected from the group consisting of Sn, Hf and Ti.

[0207] (Note 4)

[0208] The substrate processing method according to any one of Appendixes 1 to 3, wherein in the step (b), the metal-containing film is formed so that a composition ratio of the metal changes in a stepwise or continuous manner upward from the base film.

[0209] (Note 5)

[0210] A substrate processing method as described in any one of Notes 1 to 4, wherein the step (b1) and the step (b2) each include a step of applying a solution on the substrate, and the concentration of the metal in the solution used in the step (b2) is lower than the concentration of the metal in the solution used in the step (b1).

[0211] (Note 6)

[0212] In the substrate processing method according to Supplementary Note 5, the step (b1) includes a step of heating the substrate coated with the solution.

[0213] (Note 7)

[0214] The substrate processing method according to Note 5 or 6, wherein the step (b2) includes a step of heating the substrate coated with the solution.

[0215] (Note 8)

[0216] A substrate processing method as described in any one of Notes 1 to 4, wherein the step (b1) and the step (b2) each include a step of providing a mixed gas containing a metal-containing gas and an oxidizing gas to the substrate, and the ratio of the flow rate of the metal-containing gas to the total flow rate of the mixed gas or the total flow rate of the mixed gas is lower in the step (b2) than in the step (b1).

[0217] (Note 9)

[0218] A substrate processing method as described in any one of Notes 1 to 4, wherein the step (b1) and the step (b2) each include a step of alternately supplying a first gas containing a metal-containing gas and a second gas containing an oxidizing gas, and the ratio of the flow rate of the first gas to the flow rate of the second gas or the total flow rate of the first gas and the second gas is lower in the step (b2) than in the step (b1).

[0219] (Note 10)

[0220] The substrate processing method as described in Note 8 or 9, wherein the metal-containing gas contains a metal-containing organic precursor.

[0221] (Note 11)

[0222] The substrate processing method as described in any one of Notes 8 to 10, wherein the oxidizing gas includes at least one selected from H2O gas, H2O2 gas, O3 gas and O2 gas.

[0223] (Note 12)

[0224] The substrate processing method as described in any one of Notes 8 to 11, wherein:

[0225] In the step (a), the substrate is provided on a substrate support.

[0226] The temperature of the substrate supporting portion in the step (b2) is lower than the temperature of the substrate supporting portion in the step (b1).

[0227] (Note 13)

[0228] The substrate processing method as described in any one of Notes 8 to 12, wherein the step (b1) includes a step of heating the substrate.

[0229] (Note 14)

[0230] The substrate processing method as described in any one of Notes 8 to 13, wherein the step (b2) includes a step of heating the substrate.

[0231] (Note 15)

[0232] A substrate processing method as described in any one of Notes 1 to 14, wherein the step (b) includes: a step (b3) of forming one or more resist films containing the metal in a composition ratio different from that of the first resist film and the second resist film on the second resist film.

[0233] (Note 16)

[0234] The substrate processing method as described in any one of Notes 1 to 15, further comprising a step (c) of heating the substrate after the step (b).

[0235] (Note 17)

[0236] The substrate processing method as described in any one of Notes 1 to 16, further comprising a step (d) of exposing the substrate after the step (b) to form an exposed first area and an unexposed second area in the metal-containing resist film.

[0237] (Note 18)

[0238] The substrate processing method according to Supplementary Note 17 further comprises a step (e) of developing the substrate after the step (d) to selectively remove the second region from the metal-containing resist film.

[0239] (Note 19)

[0240] A substrate processing method, comprising:

[0241] Step (a), providing a substrate, wherein the substrate has a base film and a metal-containing resist film on the base film, the metal-containing resist film includes a first resist film containing metal on the base layer, and a second resist film containing the metal at a composition ratio different from that of the first resist film on the first resist film, the metal-containing resist film including a first area to be exposed and a second area to be unexposed; and

[0242] Step (b) is to develop the substrate to selectively remove the second region from the metal-containing resist film.

[0243] (Note 20)

[0244] The substrate processing method according to Supplementary Note 18 or 19 further comprises a step (f) of etching the base film after developing the substrate to selectively remove the second region from the metal-containing resist film.

[0245] (Note 21)

[0246] A substrate processing system comprises one or more substrate processing devices and a control unit, wherein:

[0247] The control unit is configured to enable the one or more substrate processing devices to execute control including control (a) and control (b), wherein:

[0248] In the control (a), a substrate having a base film is provided,

[0249] In the control (b), a metal-containing resist film is formed on the base film,

[0250] The control (b) includes:

[0251] Control (b1), forming a first resist film containing a metal on the base film; and

[0252] Control (b2) forms a second resist film containing the metal at a composition ratio different from that of the first resist film on the first resist film.

[0253] (Note 22)

[0254] A substrate processing system comprises one or more substrate processing devices and a control unit, wherein:

[0255] The control unit is configured to enable the one or more substrate processing devices to execute:

[0256] Control (a), providing a substrate, wherein the substrate has a base film and a metal-containing resist film on the base film, the metal-containing resist film includes a first resist film containing metal on the base layer, and a second resist film containing the metal at a composition ratio different from that of the first resist film on the first resist film, the metal-containing resist film including a first area to be exposed and a second area not to be exposed; and

[0257] Control (b), developing the substrate to selectively remove the second region from the metal-containing resist film.

[0258] (Note 23)

[0259] A device manufacturing method, comprising:

[0260] Step (a), providing a substrate having a base film; and

[0261] Step (b), forming a metal-containing resist film on the base film, wherein:

[0262] The step (b) comprises:

[0263] Step (b1), forming a first resist film containing a metal on the base film; and

[0264] The step (b2) is to form a second resist film on the first resist film, the second resist film containing the metal at a composition ratio different from that of the first resist film.

[0265] (Note 24)

[0266] A program for causing a computer of a substrate processing system having one or more substrate processing devices and a control unit to execute:

[0267] Control (a), providing a substrate having a base film; and

[0268] Control (b), forming a metal-containing resist film on the base film, wherein:

[0269] The control (b) includes:

[0270] Control (b1), forming a first resist film containing a metal on the base film; and

[0271] Control (b2) forms a second resist film containing the metal at a composition ratio different from that of the first resist film on the first resist film.

[0272] (Note 25)

[0273] A storage medium storing the program described in Note 24.

[0274] The above embodiments are described for the purpose of explanation and are not intended to limit the scope of the present invention. Various modifications can be implemented in each embodiment without exceeding the scope and purpose of the present invention. For example, a part of the constituent elements of one embodiment can be added to other embodiments. In addition, a part of the constituent elements of one embodiment can be replaced with corresponding constituent elements of other embodiments.

[0275] Description of Reference Numerals

[0276] 1... plasma processing device, 2... control unit, 10... plasma processing chamber, 1... substrate supporting portion, 20... gas supply portion, 30... power supply, 100... heat processing device, 102... processing chamber, 120... stage heater, 121... substrate supporting portion, 141... gas nozzle, 200... control unit, 300... liquid processing device, 311... rotating suction cup, 321... cup-shaped portion, 331... processing liquid supply nozzle, 351... cleaning liquid supply nozzle, 400... control unit, OP... opening, RM... metal-containing resist film, RM1... first resist film, RM2... second resist film, UF... base film, W... substrate.

Claims

1. A substrate processing method, characterized in that: include: Step (a), providing a substrate having a base film; and Step (b), forming a metal-containing resist film on the base film, wherein: The step (b) comprises: Step (b1), forming a first resist film containing a metal on the base film; and The step (b2) is to form a second resist film on the first resist film, the second resist film containing the metal at a composition ratio different from that of the first resist film.

2. The substrate processing method according to claim 1, characterized in that: The composition ratio of the metal in the second resist film is lower than the composition ratio of the metal in the first resist film.

3. The substrate processing method according to claim 1, characterized in that: The metal-containing resist film contains at least one metal selected from the group consisting of Sn, Hf, and Ti.

4. The substrate processing method according to claim 1, characterized in that: In the step (b), the metal-containing resist film is formed so that the composition ratio of the metal changes in a stepwise or continuous manner upward from the base film.

5. The substrate processing method according to claim 1, characterized in that: The step (b1) and the step (b2) each include a step of coating a solution on the substrate, and the composition ratio of the metal-containing precursor in the solution used in the step (b2) is lower than the composition ratio of the metal-containing precursor in the solution used in the step (b1).

6. The substrate processing method according to claim 5, characterized in that: The step (b1) includes heating the substrate coated with the solution.

7. The substrate processing method according to claim 5, characterized in that: The step (b2) includes heating the substrate coated with the solution.

8. The substrate processing method according to claim 1, characterized in that: The steps (b1) and (b2) each include a step of providing a mixed gas comprising a metal-containing gas and an oxidizing gas to the substrate, wherein the ratio of the flow rate of the metal-containing gas to the total flow rate of the mixed gas or the total flow rate of the mixed gas is lower in the step (b2) than in the step (b1).

9. The substrate processing method according to claim 1, characterized in that: The steps (b1) and (b2) each include a step of alternately supplying a first gas containing a metal-containing gas and a second gas containing an oxidizing gas, wherein a ratio of a flow rate of the first gas to a flow rate of the second gas or a total flow rate of the first gas and the second gas is lower in the step (b2) than in the step (b1).

10. The substrate processing method according to claim 8 or 9, characterized in that: The metal-containing gas comprises a metal-containing organic precursor.

11. The substrate processing method according to claim 8 or 9, characterized in that: The oxidizing gas includes at least one selected from H2O gas, H2O2 gas, O3 gas and O2 gas.

12. The substrate processing method according to claim 8 or 9, characterized in that: In the step (a), the substrate is provided on a substrate support. The temperature of the substrate supporting portion in the step (b2) is lower than the temperature of the substrate supporting portion in the step (b1).

13. The substrate processing method according to claim 8 or 9, characterized in that: The step (b1) includes heating the substrate.

14. The substrate processing method according to claim 8 or 9, characterized in that: The step (b2) includes heating the substrate.

15. The substrate processing method according to claim 1, characterized in that: The step (b) comprises: In step (b3), one or more resist films containing the metal at a composition ratio different from that of the first resist film and the second resist film are formed on the second resist film.

16. The substrate processing method according to claim 1, characterized in that: Also includes: Step (c) of heating the substrate after the step (b).

17. The substrate processing method according to claim 1, characterized in that: Also includes: Step (d), exposing the substrate after step (b) to form an exposed first region and an unexposed second region on the metal-containing resist film.

18. The substrate processing method according to claim 17, characterized in that: Also includes: Step (e) of developing the substrate after step (d) to selectively remove the second region from the metal-containing resist film.

19. A substrate processing method, characterized in that: include: Step (a), providing a substrate, wherein the substrate has a base film and a metal-containing resist film on the base film, the metal-containing resist film includes a first resist film on the base layer containing metal, and a second resist film on the first resist film containing the metal in a composition ratio different from that of the first resist film, the metal-containing resist film including a first area to be exposed and a second area to be unexposed; and Step (b) is to develop the substrate to selectively remove the second region from the metal-containing resist film.

20. The substrate processing method according to claim 18 or 19, characterized in that: Also includes: Step (f) of etching the base film after developing the substrate to selectively remove the second region from the metal-containing resist film.

21. A substrate processing system, comprising one or more substrate processing devices and a control unit, characterized in that: The control unit is configured to enable the one or more substrate processing devices to execute control including control (a) and control (b), wherein: In the control (a), a substrate having a base film is provided, In the control (b), a metal-containing resist film is formed on the base film, The control (b) includes: Control (b1), forming a first resist film containing a metal on the base film; and Control (b2) forms a second resist film containing the metal at a composition ratio different from that of the first resist film on the first resist film.

22. A substrate processing system, comprising one or more substrate processing devices and a control unit, characterized in that: The control unit is configured to enable the one or more substrate processing devices to execute: Control (a), providing a substrate, wherein the substrate has a base film and a metal-containing resist film on the base film, the metal-containing resist film includes a first resist film containing metal on the base layer, and a second resist film containing the metal at a composition ratio different from that of the first resist film on the first resist film, the metal-containing resist film including a first area to be exposed and a second area not to be exposed; and Control (b), developing the substrate to selectively remove the second region from the metal-containing resist film.

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