Substrate processing method and substrate processing system

Abstract

Provided is a technology for reducing residue in developed patterns.　Provided is a substrate processing method. This method comprises: (a) a step for providing a substrate having a base film and a metal-containing resist film formed on the base film on a substrate support part in a chamber, the metal-containing resist film having an exposed first region and an unexposed second region; and (b) a step for supplying a processing gas to the chamber to develop the substrate and selectively removing the second region from the metal-containing resist film. The (b) step includes: (b1) a step for performing development by controlling the temperature of the substrate or the substrate support part to a first temperature; and (b2) a step for performing development by controlling the temperature of the substrate or the substrate support part to a second temperature different from the first temperature.

Description

[Technical Field]

[0001] SUMMARY Exemplary embodiments of the present disclosure relate to a substrate processing method and a substrate processing system. [Background technology]

[0002] Patent Document 1 discloses a technique for forming a thin film that can be patterned on a semiconductor substrate using extreme ultraviolet light (hereinafter referred to as "EUV light"). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Special Publication No. 2021-523403 Summary of the Invention [Problem to be solved by the invention]

[0004] The present disclosure provides a technique for suppressing residues in developed patterns. [Means for solving the problem]

[0005] In one exemplary embodiment of the present disclosure, there is provided a substrate processing method including: (a) providing a substrate having an underlayer film and a metal-containing resist film formed on the underlayer film on a substrate support in a chamber, the metal-containing resist film having a first exposed region and a second unexposed region; and (b) supplying a processing gas to the chamber to develop the substrate and selectively remove the second region from the metal-containing resist film, wherein the step (b) includes: (b1) controlling the temperature of the substrate support to a first temperature to perform development; and (b2) controlling the temperature of the substrate support to a second temperature different from the first temperature to perform development. [Effects of the Invention]

[0006] According to one exemplary embodiment of the present disclosure, a technique for suppressing residues in developed patterns can be provided. [Brief explanation of the drawings]

[0007] [Figure 1A] FIG. 1 is a diagram illustrating an example of the configuration of a heat treatment system. [Figure 1B] FIG. 10 is a plan view showing another example of the configuration of the substrate support portion. [Figure 2] FIG. 1 is a diagram for explaining a configuration example in which the plasma processing system is used as a development processing system. [Figure 3] FIG. 1 is a diagram illustrating an example of the configuration of a capacitively coupled plasma processing apparatus. [Figure 4] 1 is a flowchart showing the present processing method. [Figure 5] 1 is a diagram showing an example of a cross-sectional structure of a substrate W provided in step ST11. FIG. [Figure 6] 1 is a diagram showing an example of an undercoat film UF of a substrate W. FIG. [Figure 7] 1 is a diagram showing an example of an undercoat film UF of a substrate W. FIG. [Figure 8] 10 is a diagram showing an example of a cross-sectional structure of the substrate W after processing in step ST12. FIG. [Figure 9] FIG. 10 is a diagram for explaining an example of step ST12. [Figure 10] 10 is a diagram schematically showing an example of a phenomenon occurring on the surface of the substrate W in the example shown in FIG. 9. FIG. [Figure 11] FIG. 10 is a diagram for explaining an example of step ST12. [Figure 12] FIG. 10 is a diagram for explaining an example of step ST12. [Figure 13] 10 is a flowchart according to a modified example of the present processing method. [Figure 14] FIG. 10 is a diagram for explaining an example of step ST12 in the modified example. [Figure 15] FIG. 10 is a diagram for explaining an example of step ST12 in the modified example. [Figure 16]FIG. 1 is a diagram showing the results of development according to Example 1 and Reference Example 1. [Figure 17] FIG. 2 is a block diagram for explaining an example of the configuration of a substrate processing system SS. [Figure 18] 1 is a flowchart illustrating a method MT. DETAILED DESCRIPTION OF THE INVENTION

[0008] Hereinafter, each embodiment of the present disclosure will be described.

[0009] In one exemplary embodiment, a substrate processing method is provided, comprising: (a) providing a substrate having an underlayer and a metal-containing resist film formed on the underlayer on a substrate support in a chamber, the metal-containing resist film having a first exposed region and a second unexposed region; and (b) supplying a processing gas to the chamber to develop the substrate and selectively remove the second region from the metal-containing resist film, wherein the step (b) comprises: (b1) controlling the temperature of the substrate or the substrate support to a first temperature to perform development; and (b2) controlling the temperature of the substrate or the substrate support to a second temperature different from the first temperature to perform development.

[0010] In one exemplary embodiment, the second temperature is greater than the first temperature.

[0011] In one exemplary embodiment, in step (b2), no processing gas is supplied to the chamber, or the flow rate of the processing gas supplied to the chamber is lower than the flow rate of the processing gas supplied to the chamber in step (b1).

[0012] In one exemplary embodiment, the pressure in the chamber in step (b2) is lower than the pressure in the chamber in step (b1).

[0013] In one exemplary embodiment, step (b) further includes the step of purging the processing gas in the chamber between steps (b1) and (b2).

[0014] In one exemplary embodiment, in steps (b1) and (b2), a processing gas is supplied to the chamber at a constant flow rate.

[0015] In one exemplary embodiment, a substrate processing method is provided, comprising: (a) providing a substrate having an underlayer and a metal-containing resist film formed on the underlayer to a substrate support in a chamber, the metal-containing resist film having a first exposed region and a second unexposed region; and (b) supplying a processing gas into the chamber to develop the substrate and selectively remove either the first region or the second region from the metal-containing resist film, wherein the step (b) comprises: (b1) developing the substrate under first developing conditions; and (b2) developing the substrate under second developing conditions different from the first developing conditions, the second developing conditions being different from the first developing conditions in at least one of development parameters including a temperature of the substrate or the substrate support, a pressure in the chamber, a flow rate of the processing gas, a type of the processing gas, and a residence time of the processing gas on the substrate.

[0016] In one exemplary embodiment, in step (b), the development is performed using plasma generated from the processing gas, and the development parameters further include a power level of a source RF signal for plasma generation supplied to the chamber and a power or voltage level of a bias signal supplied to the chamber.

[0017] In one exemplary embodiment, the bias signal includes a bias RF signal or a voltage pulse, and the development parameters further include at least one of a frequency of the source RF signal, a frequency of the bias RF signal, and a frequency of the voltage pulse.

[0018] In one exemplary embodiment, at least one of the source RF signal and the bias RF signal is pulsed, and the development parameters further include at least one of a duty ratio of the pulsed source RF signal and a duty ratio of the pulsed bias signal.

[0019] In one exemplary embodiment, in step (b2), the second development conditions differ from the first development conditions in two or more of the development parameters.

[0020] In one exemplary embodiment, in step (b), steps (b1) and (b2) are repeated.

[0021] In one exemplary embodiment, in step (b), a cycle including steps (b1) and (b2) is carried out one or more times, and then step (b1) is further carried out.

[0022] In one exemplary embodiment, step (b) includes performing a cycle including steps (b1) and (b2) one or more times without generating plasma from the processing gas, and then performing a cycle including steps (b1) and (b2) one or more times with generating plasma from the processing gas.

[0023] In one exemplary embodiment, step (b) includes performing a cycle including steps (b1) and (b2) one or more times while generating plasma from the processing gas, and then performing a cycle including steps (b1) and (b2) one or more times without generating plasma from the processing gas.

[0024] In at least one of the steps (b1) and (b2), the first region or the second region is selectively removed using plasma generated from a processing gas.

[0025] In one exemplary embodiment, the metal-containing resist film comprises at least one metal selected from the group consisting of Sn, Hf, and Ti.

[0026] In one exemplary embodiment, the process gas comprises a halogen-containing gas.

[0027] In one exemplary embodiment, the acidity of the treatment gas used in step (b1) is different from the acidity of the treatment gas used in step (b2).

[0028] In one exemplary embodiment, step (c) is performed in a chamber different from the chamber used for step (b).

[0029] In one exemplary embodiment, step (c) is performed in the chamber used for step (b).

[0030] In one exemplary embodiment, the first region is EUV exposed.

[0031] The temperature of the substrate or the substrate support is controlled by at least one selected from the group consisting of the output of a heater in the substrate support, the output of a heater in a side wall of a chamber that houses the substrate support, the output of a heater in the ceiling of the chamber, the temperature of a heat transfer fluid flowing in the substrate support, the pressure of a heat transfer gas supplied between the back surface of the substrate and the front surface of the substrate support, and the output of an electromagnetic wave configured to be irradiated onto the front surface of the substrate.

[0032] In one exemplary embodiment, there is provided a substrate processing system having a substrate processing apparatus with a chamber and a controller, wherein the controller is configured to control the substrate processing apparatus to (a) provide a substrate having an underlayer film and a metal-containing resist film formed on the underlayer film to a substrate support of the chamber, wherein the metal-containing resist film has a first exposed area and a second unexposed area, and (b) supply a processing gas to the chamber to develop the substrate and selectively remove the second area from the metal-containing resist film, wherein the control of (b) includes: (b1) controlling the temperature of the substrate or the substrate support to a first temperature to perform development; and (b2) controlling the temperature of the substrate or the substrate support to a second temperature different from the first temperature to perform development.

[0033] Hereinafter, each embodiment of the present disclosure will be described in detail with reference to the drawings. In each drawing, the same or similar elements are designated by the same reference numerals, and redundant explanations will be omitted. Unless otherwise specified, the positional relationships, such as up, down, left, and right, will be described based on the positional relationships shown in the drawings. The dimensional ratios in the drawings do not represent actual ratios, and the actual ratios are not limited to the ratios shown in the drawings.

[0034] <Example of heat treatment system configuration> 1A is a diagram illustrating an example of the configuration 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 treatment system, and the heat treatment apparatus 100 is an example of a substrate treatment apparatus.

[0035] The heat treatment apparatus 100 has a processing chamber 102 configured to be able to form a sealed space. The processing chamber 102 is, for example, an airtight cylindrical container configured to be able to adjust the internal atmosphere. A sidewall heater 104 is provided on the sidewall of the processing chamber 102. A ceiling heater 130 is provided on the ceiling wall (top plate) of the processing chamber 102. A ceiling surface 140 of the ceiling wall (top plate) of the processing chamber 102 is formed as a horizontal, flat surface, and its temperature is adjusted by the ceiling heater 130.

[0036] A substrate support 121 is provided at the lower side of the processing chamber 102. The substrate support 121 has a substrate support surface on which the substrate W is supported. The substrate support 121 is formed, for example, in a circular shape in a plan view, and the substrate W is placed on its horizontally formed surface (top surface). A stage heater 120 is embedded within the substrate support 121. This stage heater 120 can heat the substrate W placed on the substrate support 121. A ring assembly (not shown) may be arranged in the substrate support 121 to surround the substrate W. The ring assembly may include one or more annular members. By arranging the ring assembly around the substrate W, temperature controllability in the outer peripheral region of the substrate W can be improved. The ring assembly may be made of an inorganic material or an organic material depending on the desired heat treatment.

[0037] FIG. 1B is a plan view showing another example of the configuration of the substrate support unit. In one embodiment, the substrate support unit 121 shown in FIG. 1A may be replaced with a substrate support unit 121a shown in FIG. 1B. The substrate support unit 121a shown in FIG. 1B has multiple zones, each equipped with a heater electrode. In the example shown in FIG. 1B, the substrate support unit 121a has zones Z1 to Z14, each equipped with a heater electrode. The heater electrodes in each zone are configured to be able to receive power independently. That is, the substrate support unit 121a is configured to be able to control the temperature independently for each zone. Therefore, the substrate support unit 121a can improve the in-plane uniformity of the development of the resist film RM, which will be described later. The substrate support unit 121a can also heat the substrate W sequentially from the center toward the edge, or from the edge toward the center. Furthermore, the substrate support unit 121a can also heat a specific region of the substrate W to a higher temperature than other regions.

[0038] The substrate support 121 is supported within the processing chamber 102 by support columns 122 provided on the bottom surface of the processing chamber 102. A plurality of lift pins 123 that can be raised and lowered vertically are provided on the circumferential outer sides of the support columns 122. Each of the lift pins 123 is inserted into a through hole provided in the substrate support 121. The lift pins 123 are arranged at intervals in the circumferential direction. The lifting and lowering movement of the lift pins 123 is controlled by a lifting mechanism 124. When the lift pins 123 protrude from the surface of the substrate support 121, the substrate W can be transferred between a transport mechanism (not shown) and the substrate support 121.

[0039] An exhaust port 131 having an opening is provided in the sidewall 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, a valve, etc., and adjusts the exhaust flow rate from the exhaust port 131. The pressure inside the processing chamber 102 is adjusted by adjusting the exhaust flow rate, etc., using the exhaust mechanism 132. Note that a transfer port for a substrate W (not shown) that can be opened and closed is formed in the sidewall of the processing chamber 102 at a position different from the position where the exhaust port 131 opens.

[0040] Furthermore, a gas nozzle 141 is provided on the sidewall of the processing chamber 102 at a position different from the exhaust port 131 and the transfer port for the substrate W. The gas nozzle 141 supplies processing gas into the processing chamber 102. The gas nozzle 141 is provided on the sidewall of the processing chamber 102 on the opposite side from the exhaust port 131 when viewed from the center of the substrate support 121. That is, the gas nozzle 141 is provided on the sidewall of the processing chamber 102 symmetrically to the exhaust port 131 with respect to a vertical imaginary plane that passes through the center of the substrate support 121.

[0041] The gas nozzle 141 is formed in a rod shape that protrudes from the sidewall of the processing chamber 102 toward the center of the processing chamber 102. The tip of the gas nozzle 141 extends, for example, horizontally from the sidewall of the processing chamber 102. The processing gas is discharged into the processing chamber 102 from a discharge port opening at the tip of the gas nozzle 141, flows in the direction of the dashed-dotted arrow shown in FIG. 1A, and is exhausted from the exhaust port 131. The exhaust port 131 may be provided on the bottom surface of the processing chamber 102. The tip of the gas nozzle 141 may have a shape that extends obliquely downward toward the substrate W, or may have a shape that extends obliquely upward toward a ceiling surface 140 of the processing chamber 102.

[0042] The gas nozzle 141 may be provided, for example, on the ceiling wall of the processing chamber 102. A plurality of gas nozzles 141 may be provided on the ceiling wall. Alternatively, instead of the gas nozzle, a configuration similar to the shower head 13 shown in FIG. 3, which will be described later, may be provided. The flow rate and type of gas supplied to the substrate W from the plurality of gas nozzles or shower head may be configured to be controllable for each region of the substrate W (e.g., zones Z1 to Z14 in FIG. 1B). In one embodiment, the flow rate of gas supplied to the central region of the substrate W may be set higher than the flow rate of gas supplied to the outer regions of the substrate W.

[0043] The heat treatment apparatus 100 has a gas supply pipe 152 connected to a gas nozzle 141 from outside 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 rate controller. The gas supply unit may include a vaporizer that vaporizes a liquid material.

[0044] The control unit 200 processes computer-executable instructions that cause the heat treatment apparatus 100 to perform the various steps described in this disclosure. The control unit 200 may be configured to control each element of the heat treatment apparatus 100 to perform the various steps described herein. In one embodiment, part or all of the control unit 200 may be included in the heat treatment apparatus 100. The control unit 200 may include a processing unit 200a1, a storage unit 200a2, and a communication interface 200a3. The control unit 200 is implemented, for example, by the computer 200a. The processing unit 200a1 may be configured to read a program from the storage unit 200a2 and execute the read program to perform various control operations. This program may be stored in the storage unit 200a2 in advance or may be acquired via a medium when needed. The acquired program is stored in the storage unit 200a2 and read from the storage unit 200a2 by the processing unit 200a1 and executed. The medium may be various storage media readable by the computer 200a or 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), an 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).

[0045] <Configuration example of plasma processing system> FIG. 2 is a diagram illustrating an example of the configuration of a plasma processing system used as a development 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 simply referred to as a "processing chamber") 10, a substrate support 11, and a plasma generation unit 12. The plasma processing chamber 10 has a plasma processing space. The plasma processing chamber 10 also 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 a gas supply unit 20 (described later), and the gas exhaust port is connected to an exhaust system 40 (described later). The substrate support 11 is disposed in the plasma processing space and has a substrate support surface for supporting a substrate.

[0046] The plasma generating unit 12 is configured to generate plasma from at least one processing gas supplied into the plasma processing space. The plasma formed in the plasma processing space may be capacitively coupled plasma (CCP), inductively coupled plasma (ICP), electron-cyclotron-resonance plasma (ECR plasma), helicon wave plasma (HWP), or surface wave plasma (SWP). Various types of plasma generating units may be used, including alternating current (AC) plasma generating units and direct current (DC) plasma generating units. In one embodiment, the AC signal (AC power) used in the AC plasma generating unit has a frequency in the range of 100 kHz to 10 GHz. Therefore, the AC signal includes a radio frequency (RF) signal and a microwave signal. In one embodiment, the RF signal has a frequency in the range of 100 kHz to 150 MHz.

[0047] The control unit 2 processes computer-executable instructions that cause the plasma processing apparatus 1 to perform the various steps described in this disclosure. The control unit 2 may be configured to control each element of the plasma processing apparatus 1 to perform the various steps described herein. In one embodiment, some or all of the control unit 2 may be included in the plasma processing apparatus 1. The control unit 2 is realized by, for example, a computer 2a. The control unit 2 may include a processing unit 2a1, a memory unit 2a2, and a communication interface 2a3. Each component of the control unit 2 may be similar to each component of the control unit 200 (see FIG. 1A) described above.

[0048] The following describes a configuration example of a capacitively coupled plasma processing apparatus as an example of the plasma processing apparatus 1. Fig. 3 is a diagram for explaining a configuration example of a capacitively coupled plasma processing apparatus.

[0049] The capacitively coupled plasma processing apparatus 1 includes a plasma processing chamber 10, a gas supply 20, a power supply 30, and an exhaust system 40. The plasma processing apparatus 1 also includes a substrate support 11 and a gas inlet. The gas inlet is configured to introduce at least one process gas into the plasma processing chamber 10. The gas inlet includes a showerhead 13. The substrate support 11 is disposed within the plasma processing chamber 10. The showerhead 13 is disposed above the substrate support 11. In one embodiment, the showerhead 13 forms 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 showerhead 13, a sidewall 10a of the plasma processing chamber 10, and the substrate support 11. The plasma processing chamber 10 is grounded. The showerhead 13 and the substrate support 11 are electrically insulated from the housing of the plasma processing chamber 10.

[0050] The substrate support 11 includes a main body 111 and a ring assembly 112. The main body 111 has a central region 111a for supporting a substrate W and an annular region 111b for supporting the ring assembly 112. A wafer is an example of a substrate W. The annular region 111b of the main body 111 surrounds the central region 111a of the main body 111 in a plan view. The substrate W is disposed on the central region 111a of the main body 111, and the ring assembly 112 is disposed on the annular region 111b of the main body 111 so as to surround the substrate W on the central region 111a of the main body 111. Therefore, the central region 111a is also called a substrate support surface for supporting the substrate W, and the annular region 111b is also called a ring support surface for supporting the ring assembly 112.

[0051] In one embodiment, the main body 111 includes a base 1110 and an electrostatic chuck 1111. The base 1110 includes a conductive member. The conductive member of the base 1110 can function as a lower electrode. The electrostatic chuck 1111 is disposed on the base 1110. The electrostatic chuck 1111 includes a ceramic member 1111a and an electrostatic electrode 1111b disposed within the ceramic member 1111a. The ceramic member 1111a has a central region 111a. In one embodiment, the ceramic member 1111a also has an annular region 111b. Note that the annular region 111b may also be provided by another member surrounding the electrostatic chuck 1111, such as an annular electrostatic chuck or an annular insulating member. In this case, the ring assembly 112 may be disposed on the annular electrostatic chuck or the annular insulating member, or may be disposed on both the electrostatic chuck 1111 and the annular insulating member. Furthermore, at least one RF / DC electrode coupled to an RF power supply 31 and / or a DC power supply 32, which will be described later, may be disposed within the ceramic member 1111a. In this case, the at least one RF / DC electrode functions as a lower electrode. When a bias RF signal and / or a DC signal, which will be described later, is supplied to the at least one RF / DC electrode, the RF / DC electrode is also called a bias electrode. Note that the conductive member of the base 1110 and the at least one RF / DC electrode may function as multiple lower electrodes. Alternatively, the electrostatic electrode 1111b may function as a lower electrode. Therefore, the substrate support 11 includes at least one lower electrode.

[0052] The ring assembly 112 includes one or more annular members. In one embodiment, the one or more annular members include one or more edge rings and at least one cover ring. The edge rings are formed of a conductive or insulating material, and the cover rings are formed of an insulating material.

[0053] The substrate support 11 may also include a temperature adjustment module 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 through the flow path 1110a. In one embodiment, the flow path 1110a is formed in the base 1110, and one or more heaters are disposed in the ceramic member 1111a of the electrostatic chuck 1111. The substrate support 11 may also include a heat transfer gas supply unit configured to supply a heat transfer gas to a gap between the back surface of the substrate W and the central region 111a. The substrate support 11 may have multiple zones, similar to the substrate support 121a shown in FIG. 1B, each of which may include a heater electrode. The heater electrodes in each zone may be configured to be independently powered. That is, the substrate support 11 may be configured to allow independent temperature control for each zone.

[0054] The showerhead 13 is configured 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 multiple gas inlets 13c. The processing gas supplied to the gas supply port 13a passes through the gas diffusion chamber 13b and is introduced into the plasma processing space 10s from the multiple gas inlets 13c. The showerhead 13 also includes at least one upper electrode. In addition to the showerhead 13, the gas introduction unit may also include one or more side gas injectors (SGIs) attached to one or more openings formed in the sidewall 10a.

[0055] 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 a corresponding gas source 21 to the showerhead 13 via a corresponding flow controller 22. Each flow controller 22 may include, for example, a mass flow controller or a pressure-controlled flow controller. Additionally, the gas supply unit 20 may include at least one flow modulation device that modulates or pulses the flow rate of the at least one process gas.

[0056] 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. This generates a plasma 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 generation unit 12. Furthermore, by supplying a bias RF signal to the at least one lower electrode, a bias potential is generated on the substrate W, and ion components in the formed plasma can be attracted to the substrate W.

[0057] In one embodiment, the RF power supply 31 includes a first RF generating unit 31a and a second RF generating unit 31b. The first RF generating unit 31a is coupled to at least one lower electrode and / or at least one upper electrode via at least one impedance matching circuit and is configured to generate a source RF signal (source RF power) for plasma generation. In one embodiment, the source RF signal has a frequency in the range of 10 MHz to 150 MHz. In one embodiment, the first RF generating unit 31a may be configured to generate multiple source RF signals having different frequencies. The generated one or more source RF signals are supplied to at least one lower electrode and / or at least one upper electrode.

[0058] The second RF generating unit 31b is coupled to at least one lower electrode via at least one impedance matching circuit and configured 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 source RF signal. In one embodiment, the bias RF signal has a frequency lower than the frequency of the 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 multiple bias RF signals having different frequencies. The generated one or more bias RF signals are supplied to at least one lower electrode. In various embodiments, at least one of the source RF signal and the bias RF signal may be pulsed.

[0059] The power supply 30 may also include a DC power supply 32 coupled to the plasma processing chamber 10. The DC power supply 32 includes a first DC generator 32a and a second DC generator 32b. In one embodiment, the first DC generator 32a is connected to at least one lower electrode and configured to generate a first DC signal. The generated first DC signal is applied to the at least one lower electrode. In one embodiment, the second DC generator 32b is connected to at least one upper electrode and configured to generate a second DC signal. The generated second DC signal is applied to the at least one upper electrode.

[0060] 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 pulses may have a rectangular, trapezoidal, triangular, or combination thereof. In one embodiment, a waveform generator for generating a sequence of voltage pulses from the DC signal is connected between the first DC generator 32a and at least one lower electrode. Thus, the first DC generator 32a and the waveform generator constitute a voltage pulse generator. When the second DC generator 32b and the waveform generator constitute a voltage pulse generator, the voltage pulse generator is connected to at least one upper electrode. The voltage pulses may have either positive or negative polarity. Furthermore, the sequence of voltage pulses may include one or more positive voltage pulses and one or more negative voltage pulses within one period. The first and second DC generating units 32a and 32b may be provided in addition to the RF power supply 31, or the first DC generating unit 32a may be provided instead of the second RF generating unit 31b.

[0061] The exhaust system 40 may be connected to, for example, a gas exhaust port 10e provided at the bottom of the plasma processing chamber 10. The exhaust system 40 may include a pressure regulating valve and a vacuum pump. The pressure regulating valve regulates the pressure in the plasma processing space 10s. The vacuum pump may include a turbomolecular pump, a dry pump, or a combination thereof.

[0062] <Example of substrate processing method> FIG. 4 is a flowchart showing a substrate processing method (hereinafter also referred to as "this processing method") according to an illustrative embodiment. As shown in FIG. 4, this processing method includes a step ST11 of providing a substrate and a step ST12 of developing the substrate. This processing method may be performed in a thermal processing system (see FIG. 1A) or a plasma processing system (see FIGS. 2 and 3). The following describes an example in which the control unit 200 controls each unit of the thermal processing apparatus 100 to perform this processing method on a substrate W.

[0063] (Process ST11: Providing the substrate) First, in step ST11, a substrate W is provided in the processing chamber 102 of the heat treatment apparatus 100. The substrate W is provided on the substrate support 121 via lift pins 123. After the substrate W is placed on the substrate support 121, the temperature of the substrate W or the substrate support 121 is adjusted to a given set temperature. The temperature adjustment of the substrate W or the substrate support 121 may be performed by controlling the output of one or more heaters selected from the sidewall heater 104, the stage heater 120, the ceiling heater 130, and the piping heater 160 (hereinafter collectively referred to as "each heater"). In one example, the temperature of the substrate support 121 may be adjusted to the set temperature before step ST11. That is, the substrate W may be provided on the substrate support 121 after the temperature of the substrate support 121 is adjusted to the set temperature.

[0064] 5 is a diagram showing an example of the cross-sectional structure of the substrate W provided in step ST11. The substrate W includes an underlayer UF and a resist film RM formed on the underlayer UF. The substrate W may be used in the manufacture of semiconductor devices. The semiconductor devices include, for example, memory devices such as DRAMs and 3D-NAND flash memories, and logic devices.

[0065] 5, the resist film RM has an exposed first region RM1 and an unexposed second region RM2. The first region RM1 is an EUV-exposed region that has been exposed to EUV. The second region RM2 is an unexposed region that has not been exposed to EUV. The film thickness of the first region RM1 may be smaller than the film thickness of the second region RM2.

[0066] The resist film RM is a metal-containing resist film containing a metal. For example, the metal may include at least one metal selected from the group consisting of Sn, Hf, and Ti. For example, the resist film RM contains Sn and may include tin oxide (SnO) and tin hydroxide (Sn—OH bond). The resist film RM may further include an organic substance.

[0067] The underlayer UF may be an organic film, a dielectric film, a metal film, a semiconductor film, or a laminate film thereof formed on a silicon wafer. In one embodiment, the underlayer UF includes at least one film selected from the group consisting of a silicon-containing film, a carbon-containing film, and a metal-containing film.

[0068] 6 and 7 are diagrams showing examples of an undercoat film UF of a substrate W. As shown in Fig. 6, the undercoat film UF may be composed of a first film UF1, a second film UF2, and a third film UF3. As shown in Fig. 7, the undercoat film UF may be composed of a second film UF2 and a third film UF3.

[0069] The first film UF1 is, for example, a spin-on-glass (SOG) film, a SiC film, a SiON film, a Si-containing anti-reflective coating (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 carbonitride film, a polycrystalline silicon film, or a carbon-containing silicon film. The third film UF3 may be composed of multiple types of stacked silicon-containing films. For example, the third film UF3 may be composed of alternately stacked silicon oxide films and silicon nitride films. The third film UF3 may also be composed of alternately stacked silicon oxide films and polycrystalline silicon films. The third film UF3 may also be a stacked film including a silicon nitride film, a silicon oxide film, and a polycrystalline silicon film. The third film UF3 may also be composed of stacked silicon oxide films and silicon carbonitride films. The third film UF3 may also be a laminated film including a silicon oxide film, a silicon nitride film, and a silicon carbonitride film.

[0070] In one embodiment, the substrate W is formed as follows: First, a metal-containing photoresist film is formed on an underlayer that has been subjected to adhesion treatment, etc. The film formation may be performed by a dry process, a wet process such as solution application, or both a dry process and a wet process. Note that a surface modification process for the underlayer may be performed before the photoresist film is formed. After the photoresist film is formed, the substrate is subjected to a heat treatment, i.e., a post-applied bake (PAB). The pre-baked substrate may be subjected to an additional heat treatment. After the heat treatment, the substrate is transferred to an exposure tool, and the photoresist film is irradiated with EUV light through an exposure mask (reticle). This forms a substrate W having an underlayer film UF and a resist film RM having an exposed first region RM1 and an unexposed second region RM2. The first region RM1 corresponds to an opening in the exposure mask (reticle). The second region RM2 corresponds to a pattern in the exposure mask (reticle). EUV has a wavelength in the range of, for example, 10 to 20 nm. EUV may have a wavelength in the range of 11 to 14 nm, and in one example, has a wavelength of 13.5 nm. After exposure, the substrate W is transferred from the exposure tool to a heat treatment tool under controlled atmosphere and subjected to a heat treatment, i.e., a post-exposure bake (PEB). After PEB, the substrate W may be subjected to an additional heat treatment.

[0071] (Step ST12: Developing the substrate) Next, in step ST12, the resist film RM on the substrate W is developed. In this processing method, the second region RM2 may be selectively removed by development. In one embodiment, step ST12 includes step ST120 of developing the substrate at a first temperature, step ST121 of developing the substrate at a second temperature different from the first temperature, and step ST122 of determining whether a stop condition is satisfied.

[0072] (Step ST120: Developing the substrate at a first temperature) First, in step ST120, a process gas is supplied into the process chamber 102 through the gas nozzle 141. In one embodiment, the process gas contains a halogen-containing gas. The halogen-containing gas may be a gas containing a halogen-containing inorganic acid, such as an inorganic acid gas containing Br or Cl. The halogen-containing inorganic acid gas may be a gas containing hydrogen halide and / or boron halide. For example, the halogen-containing inorganic acid gas is at least one gas selected from the group consisting of HBr gas, BCl3 gas, HCl gas, HI gas, and HF gas. In one embodiment, the process gas may be a gas containing an organic acid. For example, the organic acid gas may be a gas containing at least one gas selected from the group consisting of a carboxylic acid, a β-dicarbonyl compound, and an alcohol. In one embodiment, the process gas is a gas containing a carboxylic acid. For example, the carboxylic acid may be formic acid (HCOOH), acetic acid (CH3COOH), trichloroacetic acid (CCl3COOH), monofluoroacetic acid (CFH2COOH), difluoroacetic acid (CF2 H The first process gas may be acetic acid (CFCOOH), trifluoroacetic acid (CFCOOH), chloro-difluoroacetic acid (CClFCOOH), sulfur-containing acetic acid, thioacetic acid (CHCOSH), thioglycolic acid (HSCHCOOH), trifluoroacetic anhydride ((CFCO)O), or acetic anhydride ((CHCO)O). In one embodiment, the process gas includes a β-dicarbonyl compound. Examples of the β-dicarbonyl compound include acetylacetone (CHC(O)CHC(O)CH), trichloroacetylacetone (CClC(O)CHC(O)CH), hexachloroacetylacetone (CClC(O)CHC(O)CCl), trifluoroacetylacetone CFC(O)CHC(O)CH), or hexafluoroacetylacetone (HFAc, CFC(O)CHC(O)CF). In one embodiment, the first process gas includes an alcohol. The alcohol, in one example, can be nonafluoro-tert-butyl alcohol ((CF3)3COH).

[0073] In one embodiment, the process gas is a gas containing trifluoroacetic acid. In one embodiment, the process gas contains a halogenated organic acid vapor. In one example, the process gas contains at least one selected from the group consisting of trifluoroacetic anhydride, acetic anhydride, trichloroacetic acid, CFHCOOH, CFHCOOH, chlorodifluoroacetic acid, sulfur-containing acetic acid, thioacetic acid, and thioglycolic acid. In one embodiment, the process gas is a mixed gas of a carboxylic acid and a hydrogen halide or a mixed gas of acetic acid and formic acid. In one embodiment, the process gas is a gas containing acetic acid.

[0074] In step ST120, the temperature of the substrate W or the substrate support 121 is controlled to a first temperature. The temperature of the substrate W or the substrate support 121 may be adjusted by controlling the output of one or more heaters. The first temperature may be appropriately selected within a range in which the second region RM2 is removed with a sufficient selectivity relative to the first region RM1. The first temperature may be appropriately selected depending on the type of process gas. For example, when HBr gas is used as the process gas, the first temperature may be, for example, 10°C or higher and 30°C or lower, or 10°C or higher and 20°C or lower, and is 10°C in one example. Step ST120 may be performed until a given period has elapsed or until the second region RM has been removed to a given depth. The given period may be, for example, 0.1 seconds or higher and 300 seconds or lower, 0.1 seconds or higher and 60 seconds or lower, or 60 seconds or higher and 300 seconds or lower.

[0075] (Step ST121: Developing the substrate at a second temperature) In step ST121, the temperature of the substrate W or the substrate support 121 is controlled to a second temperature different from the first temperature. The temperature of the substrate W or the substrate support 121 may be adjusted by controlling the output of one or more heaters. In one embodiment, the second temperature may be higher than the first temperature. The second temperature may be appropriately selected depending on the type of process gas. For example, when HBr gas is used as the process gas, the second temperature may be 40°C or higher and 100°C or lower, or 50°C or higher and 100°C or lower, and is 60°C in one example.

[0076] In step ST121, a process gas may be supplied into the process chamber 102 through the gas nozzle 141. In one embodiment, the flow rate of the process gas is smaller than the flow rate of the process gas in step ST120. In step ST121, the process gas does not necessarily have to be supplied into the process chamber 102.

[0077] When a process gas is supplied in step ST121, the type of the process gas may be the same as or different from the process gas in step ST120. In one embodiment, the acidity of the process gas supplied in step ST121 is lower than that of step ST120. That is, a process gas having a higher acid dissociation constant (pKa) than the process gas used in step ST120 may be used in step ST121. For example, the process gas may be changed from HBr gas or BCl3 (step ST120) to a carboxylic acid gas such as acetic acid gas (step ST121). Furthermore, in step ST121, the flow rate (partial pressure) of the process gas having a higher acid dissociation constant (pKa) may be increased compared to the flow rate (partial pressure) of the process gas used in step ST120. For example, when the process gas in steps ST120 and ST121 is a mixed gas of HBr gas and a carboxylic acid gas, the flow rate (partial pressure) of the carboxylic acid gas may be increased in step ST121.

[0078] The pressure in the processing chamber 102 in step ST121 may be the same as or different from that in step ST120. In one embodiment, the pressure in the processing chamber 102 in step ST121 is lower than the pressure in the processing chamber 102 in step ST120. For example, the pressure in the processing chamber 102 in step ST120 may be set to 50 mTorr or more and 500 mTorr or less, 50 mTorr or more and 400 mTorr or less, or 50 mTorr or more and 300 mTorr or less. For example, the pressure in the processing chamber 102 in step ST121 may be set to 0.1 mTorr or more and 100 mTorr or less.

[0079] Step ST121 may be performed until a given period of time (for example, 0.1 seconds or more and 300 seconds or less, or 0.1 seconds or more and 60 seconds or less, or 60 seconds or more and 300 seconds or less) has elapsed or until the second region RM of a given depth has been removed.

[0080] (Process ST122: Judgment) In step ST122, it is determined whether a given condition for ending step ST12 is satisfied. If it is determined in step ST122 that the given condition is not satisfied, the process returns to step ST120. If it is determined that the given condition is satisfied, step ST12 is terminated. The given condition may be, for example, that a cycle including steps ST120 and ST121 has been repeated a predetermined number of times. This number may be one or more times. The given condition may be, for example, a condition related to the development time, i.e., the time elapsed since the start of step ST12. The given condition may be, for example, a condition related to the dimensions, such as the depth or aspect ratio, of the opening or recess formed in the resist film RM after step ST121. In this case, after step ST121, it may be determined whether the dimension of the resist film RM has reached a given value or range, and the cycle of steps ST120 and ST121 may be repeated until the given value or range is reached. The dimension of the resist film RM may be measured using an optical measurement device.

[0081] In one embodiment, after a cycle including step ST120 and step ST121 has been performed one or more times, a determination as to whether a given condition is satisfied may be made not only after the end of step ST121 but also after the end of step ST120. If it is determined that the given condition is satisfied, step ST12 may be ended without performing step ST121.

[0082] In one embodiment, a step of purging the gas in the processing chamber 102 through the exhaust port 131 (hereinafter also referred to as a "purging step") may be performed between step ST120 and step ST121. At this time, an inert gas or the like may be supplied into the processing chamber 102. This purges gases of reaction products generated by development, excess processing gas, and the like.

[0083] FIG. 8 is a diagram showing an example of the cross-sectional structure of the substrate W after processing in step ST12. In the example shown in FIG. 8, the second region RM2 of the resist film RM is removed, and an opening OP is formed. The opening OP is defined by the side surface of the first region RM1. The opening OP is a space on the base film UF surrounded by the side surface. The opening OP has a shape corresponding to the second region RM2 in a plan view of the substrate W (and consequently a shape corresponding to the exposure mask pattern used for EUV exposure). The shape may be, for example, a circle, an ellipse, a rectangle, a line, or a combination of one or more of these. A plurality of openings OP may be formed in the resist film RM. Each of the plurality of openings OP may have a linear shape and may be arranged at regular intervals to form a line-and-space pattern. Alternatively, a plurality of openings OP may be arranged in a lattice pattern to form a pillar pattern.

[0084] According to this processing method, the temperature of the substrate W or the substrate support 121 is changed between step ST120 and step ST121. This makes it possible to adjust the amount of volatilization of reaction products generated during development. This can prevent a decrease in development rate due to the inability of reaction products to volatilize and the generation of residues after development.

[0085] FIG. 9 is a diagram illustrating an example of step ST12. In FIG. 9, the horizontal axis represents time. The vertical axis represents the flow rate [sccm] of the processing gas supplied to the processing chamber 102, the pressure [Torr] in the processing chamber 102, and the temperature [°C] of the substrate support 121. The processing gas flow rate "Q1" indicates that the processing gas is not being supplied or is lower than the flow rate indicated by "Q2." The processing chamber 102 pressure "P1" indicates that the pressure is lower than "P2." The substrate support 121 temperature "T1" indicates that the substrate support 121 temperature is lower than "T2." "T1" corresponds to the first temperature, and "T2" corresponds to the second temperature. FIG. 9 illustrates an example in which the processing gas flow rate and the pressure in the processing chamber 102 are kept constant, while the temperature of the substrate support 121 is alternately changed between "T1" (step ST120) and "T2" (step ST121).

[0086] 10 is a diagram schematically illustrating an example of a phenomenon occurring on the surface of the substrate W in the example illustrated in FIG. 9. In step ST120, reaction products R generated by a reaction between the resist film in the second region RM2 and the processing gas are volatilized, and the second region RM2 is removed. As development progresses and recesses formed in the resist film RM become deeper, the reaction products R may accumulate in the recesses, increasing the internal pressure and suppressing the volatilization of the reaction products R. In this regard, in the example illustrated in FIG. 9, development is performed in step ST121 by setting the temperature of the substrate support member 121 to a higher temperature (T2>T1) than in step ST120. Therefore, as illustrated in FIG. 10, the volatilization of the reaction products R is accelerated compared to step ST120. This can suppress a decrease in the development rate due to the reaction products R remaining in the recesses.

[0087] 9, low-temperature (T1) development in step ST120 and high-temperature (T2) development in step ST121 are alternately repeated, thereby preventing the development at high temperature (T2) from continuing. This prevents the first region RM1 from being excessively removed and resulting in a reduction in film thickness. In other words, the development selectivity (the ratio of the development rate of the second region RM2 to the development rate of the first region RM1, also known as development contrast) is improved.

[0088] Fig. 11 is a diagram illustrating an example of step ST12. The vertical and horizontal axes in Fig. 11 are the same as those in Fig. 9. The example shown in Fig. 11 differs from the example shown in Fig. 9 in that in step ST121, no processing gas is supplied or the processing gas is supplied at a flow rate lower than that in step ST120.

[0089] In the example shown in FIG. 11 , similar to the example shown in FIG. 9 , development is performed in step ST121 by setting the temperature of the substrate support member 121 to a higher temperature (T2>T1) than in step ST120. Therefore, volatilization of the reaction product R is accelerated compared to step ST120. This can prevent the reaction product R from remaining in the recesses and reducing the development rate. Also, in the example shown in FIG. 11 , similar to the example shown in FIG. 9 , low-temperature (T1) development in step ST120 and high-temperature (T2) development in step ST121 are alternately repeated, preventing continuous development at high temperature (T2). Also, in the example shown in FIG. 11 , the supply amount of processing gas during high-temperature (T2) development in step ST121 is reduced compared to step ST120 or is zero. This can mitigate an increase in the development rate of the first region RM1 due to an increase in the temperature of the substrate support member 121. As a result, excessive removal of the first region RM1 and a reduction in film thickness can be prevented. That is, the development selectivity (the ratio of the development speed in the second region RM2 to the development speed in the first region RM1, also called the development contrast) is improved.

[0090] 11, the timing of the increase (decrease) in the flow rate of the processing gas and the timing of the decrease (rise) in the temperature of the substrate support part coincide with each other, but the respective timings may be wholly or partially different (out of phase). That is, in step ST121, it is sufficient that the period during which the flow rate of the processing gas is Q1 and the period during which the temperature of the substrate support part is T2 overlap at least partially.

[0091] Fig. 12 is a diagram for explaining an example of step ST12. The vertical and horizontal axes in Fig. 12 are the same as those in Fig. 9. The example shown in Fig. 12 differs from the example shown in Fig. 11 in that a purge step is included between step ST120 and step ST121, and in that the pressure (P1) in the processing chamber 102 at step ST121 is lower than the pressure (P2) at step ST120.

[0092] 12, similar to the example shown in FIG. 9, development is performed in step ST121 at a higher temperature (T2>T1) of the substrate support member 121 than in step ST120. Therefore, volatilization of the reaction product R is accelerated compared to step ST120. Additionally, in the example shown in FIG. 12, a purge step is performed between step ST120 and step ST121. This prevents the reaction product R from remaining in the recesses and decreasing the development rate. Similarly to the example shown in FIG. 9, development at a low temperature (T1) in step ST120 and development at a high temperature (T2) in step ST121 are alternately repeated in the example shown in FIG. 12, thereby preventing development at a high temperature (T2) from continuing. Furthermore, in the example shown in FIG. 12, during development at a high temperature (T2) in step ST121, the supply rate of the process gas is reduced or becomes zero compared to step ST120, and the pressure in the processing chamber 102 is lower than that in step ST120. This can mitigate an increase in the development rate of the first region RM1 due to an increase in the temperature of the substrate support portion 121. As a result, excessive removal of the first region RM1 and a decrease in film thickness can be suppressed. In the example shown in FIG. 12, the timing of the increase in the flow rate of the processing gas, the increase in the pressure in the chamber, and the decrease in the temperature of the substrate support portion are synchronized, but the timing of each may be entirely or partially different (out of phase). That is, in step ST121, it is sufficient that the period during which the flow rate of the processing gas is Q1 and the period during which the temperature of the substrate support portion is T2 overlap at least partially.

[0093] In one embodiment, this processing method may be performed using a plasma processing system (see FIGS. 2 and 3). For example, a substrate W may be provided on a substrate support 11 in a processing chamber 10 of a plasma processing apparatus 1 (step ST11), and the temperature of the substrate W or the substrate support 11 may be adjusted by a temperature control module to develop the resist film RM (step ST12). The temperature of the substrate W or the substrate support 11 may be adjusted by controlling the pressure of a heat transfer gas (e.g., He) between the electrostatic chuck 1111 and the rear surface of the substrate W. The processing gas used in step ST12 may be the same as that used in a heat processing system. In step ST120 and / or step ST121, development may be performed by generating plasma from the processing gas. That is, a source RF signal may be supplied to the lower electrode of the substrate support 11 and / or the upper electrode of the shower head 13. At this time, a bias signal may be supplied to the lower electrode of the substrate support 11.

[0094] In one embodiment, the development treatment in step ST12 may be performed by both heat treatment and plasma treatment. For example, a cycle in which steps ST120 and ST121 are performed by heat treatment (hereinafter also referred to as a "heat treatment cycle") may be performed one or more times, and then a cycle in which steps ST120 and ST121 are performed by plasma treatment (hereinafter also referred to as a "plasma treatment cycle") may be performed one or more times. Alternatively, for example, a plasma treatment cycle may be performed one or more times, and then a heat treatment cycle may be performed one or more times. Alternatively, for example, a heat treatment cycle and a plasma treatment cycle may be performed multiple times alternately. Alternatively, for example, step ST120 may be performed by heat treatment and step ST121 by plasma treatment, or step ST120 may be performed by plasma treatment and step ST121 by heat treatment.

[0095] In one embodiment, in step ST12, instead of adjusting the temperature of the substrate support (substrate support 121 or substrate support 11), the substrate W may be directly heated to make the temperature of the substrate W in step ST121 different from the temperature of the substrate W in step ST120. For example, a device that generates electromagnetic waves such as infrared light or microwaves may be provided in the heat treatment device 100 or the plasma treatment device 1, and the temperature of the substrate W may be adjusted by irradiating the substrate W with electromagnetic waves using the device.

[0096] In one embodiment, the processing method may include a desorption step. The desorption step involves removing scum from the surface of the resist film RM and the surface of the underlayer UF or smoothing the surface of the resist film RM using an inert gas or plasma of the inert gas. The desorption step may be performed after step ST12. The desorption step may be repeated one or more times between developments in step ST12. The desorption step may be performed, for example, by exposing the substrate W to plasma generated in the plasma processing apparatus 1. The desorption step may be performed, for example, by introducing a processing gas excited by a remote plasma source into the processing chamber 102 of the thermal processing apparatus 100. The inert gas may be, for example, a noble gas such as He, Ar, Ne, Kr, or Xe, or nitrogen gas.

[0097] In one embodiment, the processing method may include a step of etching the base film UF after step ST12. The etching may be performed, for example, by generating plasma from a processing gas in the processing chamber 10 of the plasma processing apparatus 1. During the etching, the resist film RM functions as a mask, and recesses are formed in the base film UF based on the shape of the openings OP. Note that when development is performed using the plasma processing apparatus 1 in step ST12, the etching process may be performed consecutively in the same processing chamber 10 as step ST12, or may be performed in a processing chamber 10 of a different plasma processing apparatus 1.

[0098] 13 is a flowchart of a modified example of the present processing method. As shown in FIG. 13, step ST12 may include step ST120A of developing the substrate under first developing conditions and step ST121A of developing the substrate under second developing conditions, instead of steps ST120 and ST121 described above. This modified example may be performed in a thermal processing system (see FIG. 1A) or a plasma processing system (see FIGS. 2 and 3).

[0099] The second development conditions differ from the first development conditions in at least one development parameter. In one embodiment, the second development conditions differ by two or more development parameters. The development parameters may include the temperature of the substrate support (121, 11), the temperature of the substrate W, the pressure in the process chamber (102, 10), the flow rate of the process gas, the type of process gas, and the residence time. The residence time is the residence time of the process gas on the substrate W. The residence time is expressed as (P×V) / Q, where V is the volume of the process chamber, P is the pressure in the process chamber, and Q is the flow rate of the process gas. When the present processing method is performed using a plasma processing system (see FIGS. 2 and 3 ), the development parameters may further include the power level of a source RF signal for plasma generation supplied to the process chamber 10 and the power or voltage level of a bias signal supplied to the process chamber 10. The development parameters may further include the frequency of the source RF signal. When the source RF signal is pulsed, the development parameters may further include the duty ratio of the pulsed source RF signal. If the bias signal is a bias RF signal, the development parameters may further include the frequency of the bias RF signal. If the bias RF signal is pulsed, the development parameters may further include the duty ratio of the pulsed bias RF signal. If the bias signal includes a voltage pulse, the development parameters may further include the frequency (pulse frequency) and duty ratio of the voltage pulse.

[0100] FIG. 14 is a diagram illustrating an example of step ST12 in a modified example. In FIG. 14, the horizontal axis represents time. The vertical axis represents the flow rate [sccm] of the processing gas supplied to the processing chamber (102, 10) and the pressure [mTorr] in the processing chamber (102, 10). The processing gas flow rate "Q1" indicates that the processing gas is not being supplied or is lower than the flow rate indicated by "Q2." The processing chamber 102 pressure "P1" indicates that the pressure is lower than "P2." FIG. 14 illustrates an example in which two of the development parameters, the processing gas flow rate and the processing chamber pressure, are different between the first and second development conditions. Note that the remaining development parameters may be the same between development condition 1 and development condition 2. In the example illustrated in FIG. 14, the timing of the increase (decrease) in the processing gas flow rate and the decrease (increase) in the chamber pressure are the same, but the respective timings may be entirely or partially different (phase shifted). That is, in step ST121A, it is only necessary that the period during which the flow rate of the processing gas is Q1 and the period during which the pressure in the chamber is P2 at least partially overlap.

[0101] FIG. 15 is a diagram illustrating an example of step ST12 in a modified example. In FIG. 15, the horizontal axis represents time. The vertical axis represents the flow rates [sccm] of the first gas G1 and the second gas G2 contained in the processing gas supplied to the processing chamber (102, 10). The "Q1" for the first gas flow rate indicates that the flow rate of the first gas contained in the processing gas is zero or less than the flow rate indicated by "Q2." The "Q3" for the second gas flow rate indicates that the flow rate of the second gas contained in the processing gas is zero or less than the flow rate indicated by "Q4." FIG. 15 illustrates an example in which the types of processing gases are different from each other among the development parameters of the first and second development conditions. In one embodiment, the second gas has a higher acid dissociation constant (pKa) than the first gas. In this case, the acidity of the processing gas used in step ST121A is lower than the acidity of the processing gas used in step ST120A. The other development parameters may be the same between development condition 1 and development condition 2. In the example shown in Fig. 15, the timing of the increase (decrease) in the flow rate of the first process gas and the timing of the decrease (increase) in the flow rate of the second process gas coincide, but the respective timings may be wholly or partially different (out of phase). That is, in step ST121, it is sufficient that the period during which the flow rate of the first gas is Q1 and the period during which the flow rate of the second gas is Q4 overlap at least partially.

[0102] In the exemplary embodiment described above, the second region RM2 of the resist film RM is selectively removed relative to the first region RM1 during the development in step ST12. However, the present processing method is not limited to this. In one embodiment, the first region RM1 of the resist film RM may be selectively removed relative to the second region RM2 during the development in step ST12.

[0103] <Example> Next, examples of the present processing method will be described, but the present disclosure is not limited to the following examples.

[0104] Example 1 In Example 1, the present processing method (see FIG. 4) was applied to the substrate W (see FIG. 5) using the plasma processing apparatus 1 (see FIG. 3) to develop the resist film RM.

[0105] In step ST11, a substrate W was provided on a substrate support 11 in a processing chamber 10. The resist film RM of the substrate W was an organic film containing Sn, and had a first region RM1 that was exposed to EUV and a second region RM2 that was not exposed to EUV. The base film UF of the substrate W was a silicon oxide film. The film thickness of the second region RM2 was about 1.3 times larger than the film thickness of the first region RM1.

[0106] Step ST12 included step ST120, a purge step, and step ST122. In step ST12, a source RF signal and a bias signal were not supplied, i.e., plasma was not generated from the processing gas.

[0107] Step ST120 was performed for 60 seconds. In step ST120, the substrate support 11 was adjusted to 10° C. The process gas contained HBr gas and Ar gas. The pressure in the process chamber 10 was maintained at 200 mTorr.

[0108] The purging step was performed for 30 seconds using Ar gas, and the pressure inside the processing chamber 10 was maintained at 10 mTorr or less.

[0109] Step ST121 was performed for 60 seconds. In step ST121, the substrate support 11 was adjusted to 60° C. The processing gas contained Ar gas. The pressure inside the processing chamber 10 was maintained at 10 mTorr or less.

[0110] (Reference example 1) In Reference Example 1, the resist film RM on the substrate W (see FIG. 5) was developed using the plasma processing apparatus 1 (see FIG. 3). The development was performed continuously under the same conditions as those of step ST120 in Example 1 (temperature of the substrate support 11: 10° C., pressure of the processing chamber 10: 200 mTorr, processing gas containing HBr gas and Ar gas). That is, in Reference Example 1, unlike Example 1, the purge step and step ST121 were not performed.

[0111] FIG. 16 is a diagram showing the results of development according to Example 1 and Reference Example 1. In FIG. 16, "t [sec]" on the horizontal axis indicates the development time [seconds], and "D [au]" on the vertical axis indicates the normalized film thickness of the resist film RM (ratio to the reference thickness). E1(RM1) indicates the results for the first region RM1 of Example 1, and E1(RM2) indicates the results for the second region RM2 of Example 1. R1(RM1) indicates the results for the first region RM1 of Reference Example 1, and R1(RM2) indicates the results for the second region RM2 of Reference Example 1.

[0112] As shown in FIG. 16 , in Example 1, the second region RM2 was selectively removed through step ST120 (0 to 60 seconds), the purging step (60 to 90 seconds), step ST121 (90 to 150 seconds), and the second step ST120 (150 to 180 seconds). The film thickness of the first region RM1 was reduced only slightly, and the development contrast was maintained. In contrast, in Reference Example 1, the development rate of the second region RM2 decreased with the passage of development time, and the development contrast with the first region RM1 was no longer maintained, making it impossible to selectively remove the second region RM2. In Example 1, the inclusion of the purging step and the increase in the temperature of the substrate support 11 in step ST121 likely prevented reaction products from remaining in the recesses during development, thereby accelerating the development of the second region RM2. Furthermore, in Example 1, the process gas in step ST121 did not contain HBr gas, and the pressure in the process chamber 10 was maintained lower than that in step ST120. This is thought to have alleviated the influence of an increase in development speed due to a rise in temperature of the substrate support portion 11, and prevented the first region RM1 from being removed.

[0113] <Configuration example of substrate processing system> 17 is a block diagram illustrating an example of the configuration 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 apparatus EX, a second interface station IS2, a second processing station PS2, a second carrier station CS2, and a controller CT.

[0114] The first carrier station CS1 loads and unloads the first carrier C1 between the first carrier station CS1 and a system external to the substrate processing system SS. The first carrier station CS1 has a mounting table including a plurality of first mounting plates ST1. The first carrier C1, which may contain a plurality of substrates W or be empty, is mounted on each first mounting plate ST1. The first carrier C1 has a housing capable of housing a plurality of substrates W therein. The first carrier C1 is, for example, a front-opening unified pod (FOUP).

[0115] The first carrier station CS1 also transports the substrate W between the first carrier C1 and the first processing station PS1. The first carrier station CS1 further includes a first transport device HD1. The first transport device HD1 is provided in the first carrier station CS1 so as to be located between the mounting table and the first processing station PS1. The first transport device HD1 transports and hands over the substrate W between the first carrier C1 on each first mounting plate ST1 and the second transport device HD2 of the first processing station PS1. The substrate processing system SS may further include a load lock module. The load lock module may be provided between the first carrier station CS1 and the first processing station PS1. The internal pressure of the load lock module can be switched between atmospheric pressure and vacuum. "Atmospheric pressure" may refer to the pressure inside the first transfer device HD1. "Vacuum" refers to a pressure lower than atmospheric pressure, and may be a medium vacuum of, for example, 0.1 Pa to 100 Pa. The inside of the second transport device HD2 may be atmospheric pressure or vacuum. The load lock module may, for example, transfer a substrate W from the first transport device HD1, which is at atmospheric pressure, to the second transport device HD2, which is at vacuum, and transfer a substrate W from the second transport device HD2, which is at vacuum, to the first transport device HD1, which is at atmospheric pressure.

[0116] 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 thermal processing module PM3 (hereinafter collectively referred to as "first substrate processing modules PMa"). The first processing station PS1 also includes a second transfer device HD2 that transfers the substrate W. The second transfer device HD2 transfers and passes 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.

[0117] In the pre-treatment module PM1, the substrate W is subjected to pre-treatment. In one embodiment, the pre-treatment module PM1 includes a temperature adjustment unit that adjusts the temperature of the substrate W, a high-precision temperature adjustment unit that adjusts the temperature of the substrate W with high precision, etc. In one embodiment, the pre-treatment module PM1 includes a surface modification treatment unit that performs a surface modification treatment on the substrate W. Each treatment unit in the pre-treatment module PM1 may be configured to include a heat treatment device 100 (see FIG. 1A), a plasma treatment device 1 (see FIGS. 2 and 3), and / or a liquid treatment device such as a spin coater.

[0118] In the resist film formation module PM2, a resist film is formed on the substrate W. In one embodiment, the resist film formation module PM2 includes a dry coating unit. The dry coating unit forms a resist film on the substrate W using a dry process such as a vapor phase deposition method. In one example, the dry coating unit includes a CVD apparatus or an ALD apparatus that performs chemical vapor deposition of a resist film on the substrate W arranged in a chamber, or a PVD apparatus that performs physical vapor deposition of a resist film. The dry coating unit may be a thermal processing apparatus 100 (see FIG. 1) or a plasma processing apparatus 1 (see FIGS. 2 and 3).

[0119] In one embodiment, the resist film formation module PM2 includes a wet coating unit that forms a resist film on the substrate W using a wet process such as a liquid deposition method. The wet coating unit may be, for example, a liquid processing device such as a spin coater.

[0120] In one embodiment, an example of the resist film formation module PM2 includes both a wet coating unit and a dry coating unit.

[0121] The substrate W is subjected to a thermal treatment in the first thermal treatment module PM3. In one embodiment, the first thermal treatment module PM3 includes one or more of a pre-bake (PAB) unit that performs a heat treatment on the substrate W on which a resist film has been formed, a temperature adjustment unit that adjusts the temperature of the substrate W, and a high-precision temperature adjustment unit that adjusts the temperature of the substrate W with high precision. Each of these units may have one or more thermal treatment devices. In one example, the multiple thermal treatment devices may be stacked. The thermal treatment device may be, for example, the thermal treatment device 100 (see FIG. 1A). Each thermal treatment may be performed at a predetermined temperature using a predetermined gas.

[0122] The first interface station IS1 has a third transfer device HD3. The third transfer device HD3 transfers and delivers substrates W between the first processing station PS1 and the exposure apparatus EX. The third transfer device HD3 has a housing that houses the substrates W, and may be configured so that the temperature, humidity, pressure, etc. within the housing can be controlled.

[0123] The exposure apparatus EX uses an exposure mask (reticle) to expose a resist film on the substrate W. The exposure apparatus EX may be, for example, an EUV exposure apparatus having a light source that generates EUV light.

[0124] The second interface station IS2 has a fourth transfer device HD4. The fourth transfer device HD4 transfers and delivers substrates W between the exposure apparatus EX and the second processing station PS2. The fourth transfer device HD4 has a housing that houses the substrates W, and may be configured so that the temperature, humidity, pressure, etc. within the housing can be controlled.

[0125] 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 modules PMb"). The second processing station PS2 also includes a fifth transfer device HD5 that transfers the substrate W. The fifth transfer device HD5 transfers and passes 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.

[0126] The substrate W is thermally treated in the second thermal treatment module PM4. In one embodiment, the thermal treatment module PM4 includes one or more of a post-exposure bake (PEB) unit that heat-treats the exposed substrate W, a temperature adjustment unit that adjusts the temperature of the substrate W, and a high-precision temperature adjustment unit that adjusts the temperature of the substrate W with high precision. Each of these units may have one or more thermal treatment devices. In one example, the multiple thermal treatment devices may be stacked. The thermal treatment device may be, for example, the thermal treatment device 100 (see FIG. 1A). Each thermal treatment may be performed at a predetermined temperature using a predetermined gas.

[0127] In the measurement module PM5, various measurements are performed on the substrate W. In one embodiment, the measurement module PM5 includes an imaging unit including a mounting stage for mounting the substrate W, an imaging device, an illumination device, and various sensors (temperature sensor, reflectance measurement sensor, etc.). The imaging device may be, for example, a CCD camera that captures an image of the appearance of the substrate W. Alternatively, the imaging device may be a hyperspectral camera that captures images by dispersing light into wavelengths. The hyperspectral camera can measure one or more of the pattern shape, dimensions, film thickness, composition, and film density of the resist film.

[0128] 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 that performs dry development on the substrate W. The dry developing unit may be, for example, a thermal processing apparatus 100 (see FIG. 1A) or a plasma processing apparatus 1 (see FIGS. 2 and 3).

[0129] The substrate W is subjected to a thermal treatment in the third thermal treatment module PM7. In one embodiment, the third thermal treatment module PM7 includes one or more of a post bake (PB) unit that heat-treats the substrate W after development, a temperature adjustment unit that adjusts the temperature of the substrate W, and a high-precision temperature adjustment unit that adjusts the temperature of the substrate W with high precision. Each of these units may have one or more thermal treatment devices. In one example, the multiple thermal treatment devices may be stacked. The thermal treatment device may be, for example, the thermal treatment device 100 (see FIG. 1A). Each thermal treatment may be performed at a predetermined temperature using a predetermined gas.

[0130] The second carrier station CS2 transfers the second carrier C2 between the second carrier station CS2 and a system external to the substrate processing system SS. The configuration and functions of the second carrier station CS2 may be similar to those of the first carrier station CS1 described above.

[0131] The control unit CT controls each component of the substrate processing system SS to perform a given process on the substrate W. The control unit CT stores a recipe in which the process procedure, process conditions, transport conditions, etc. are set, and controls each component of the substrate processing system SS to perform the given process on the substrate W in accordance with the recipe. The control unit CT may also have some or all of the functions of each control unit (the control unit 200, control unit 2, and control unit 400 shown in FIGS. 1A to 4).

[0132] <Example of substrate processing method> FIG. 18 is a flowchart showing a substrate processing method (hereinafter also referred to as “method MT”) according to an exemplary embodiment. As shown in FIG. 18 , method MT includes step ST100 of pre-treating a substrate, step ST200 of forming a resist film on the substrate, step ST300 of performing a heat treatment (pre-bake: PAB) on the substrate on which the resist film has been formed, step ST400 of exposing the substrate to EUV light, step ST500 of performing a heat treatment (post-exposure bake: 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-bake: PB) on the developed substrate, and step ST900 of etching the substrate. Method MT may not include one or more of the above steps. For example, method MT may not include step ST600, and step ST700 may be performed after step ST500.

[0133] The method MT may be performed using a substrate processing system SS shown in Fig. 17. In the following, an example will be described in which a control unit CT of the substrate processing system SS controls each part of the substrate processing system SS to perform the method MT on a substrate W.

[0134] (Process ST100: Pretreatment) First, a first carrier C1 containing a plurality of substrates W is loaded into a first carrier station CS1 of the substrate processing system SS. The first carrier C1 is placed on a first mounting plate ST1. Next, the first transport device HD1 sequentially removes each substrate W from the first carrier C1 and transfers them to a second transport device HD2 of the first processing station PS1. The substrates W are then transported by the second transport device HD2 to a pre-processing module PM1. The pre-processing module PM1 performs pre-processing on the substrates W. The pre-processing may include, for example, one or more of temperature adjustment of the substrates W, forming a part or all of an undercoat film on the substrates W, heating the substrates W, and high-precision temperature adjustment of the substrates W. The pre-processing may also include a surface modification process for the substrates W.

[0135] (Step ST200: Resist film formation) Next, the substrate W is transported to the resist film forming module PM2 by the second transport device HD2. A resist film is formed on the substrate W by the resist film forming module PM2. In one embodiment, the resist film is formed by a wet process. For example, a resist film is formed by spin-coating a resist film on the substrate W using a wet coating unit of the resist film forming module PM2. In one embodiment, the resist film is formed on the substrate W by a dry process such as a vapor phase deposition method. For example, a resist film is formed by vapor-depositing a resist film on the substrate W using a dry coating unit of the resist film forming module PM2.

[0136] The resist film may be formed on the substrate W 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.

[0137] (Process ST300:PAB) Next, the substrate W is transferred by the second transfer device HD2 to the first thermal treatment module PM3. The first thermal treatment module PM3 subjects the substrate W to a heat treatment (pre-baking: PAB). The pre-baking may be performed in an air atmosphere or an inert atmosphere. The pre-baking may be performed by heating the substrate W to 50°C or higher or 80°C or higher. The heating temperature of the substrate W may be 250°C or lower, 200°C or lower, or 150°C or lower. In one example, the heating temperature of the substrate may be 50°C or higher and 250°C or lower. When a resist film is formed by a dry process in step ST200, in one embodiment, the pre-baking may be performed in the dry coating unit that performed step ST200. In one embodiment, after the pre-baking, a process (Edge Bead Removal: EBR) may be performed to remove the resist film from the edge of the substrate W.

[0138] (Process ST400: EUV Exposure) Next, the substrate W is transferred by the second transfer device HD2 to the third transfer device HD3 of the first interface station IS1. Then, the substrate W is transferred by the third transfer device HD3 to the exposure apparatus EX. The substrate W undergoes EUV exposure through an exposure mask (reticle) in the exposure apparatus EX. As a result, on the substrate W, a first region that has undergone EUV exposure and a second region that has not undergone EUV exposure are formed corresponding to the pattern of the exposure mask (reticle).

[0139] (Process ST500: PEB) Next, the substrate W is transferred from the fourth transfer device HD4 of the second interface station IS2 to the fifth transfer device HD5 of the second processing station PS2. Then, the substrate W is transferred by the fifth transfer device HD5 to the second heat treatment module PM4. And, a heat treatment (post-exposure bake: PEB) is performed on the substrate W in the second heat treatment module PM4. The post-exposure bake may be performed in an air atmosphere. Also, the post-exposure bake may be performed by heating the substrate W to 180°C or higher and 250°C or lower.

[0140] (Process ST600: Measurement) Next, the substrate W is transferred by the fifth transfer device HD5 to the measurement module PM5. The measurement module PM5 measures the substrate W. The measurement may be an optical measurement or other measurement. In one embodiment, the measurement by the measurement module PM5 includes measurement of the appearance and / or dimensions of the substrate W using a CCD camera. In one embodiment, the measurement by the measurement module PM5 includes measurement of any one or more of the pattern shape, dimensions, film thickness, composition, and film density of the resist film (hereinafter also referred to as "pattern shape, etc.") using a hyperspectral camera.

[0141] In one embodiment, the control unit CT determines the presence or absence of exposure abnormality of the substrate W based on the measured appearance and dimensions of the substrate W and / or the pattern shape or the like. In one embodiment, when it is determined in the control unit CT that there is an exposure abnormality, the substrate W may be reworked or discarded without performing the development 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 again to form a resist film. Although the rework after development may involve damage to the substrate W, by performing the rework before development, damage to the substrate W can be avoided or suppressed.

[0142] (Step ST700: Development) Next, the substrate W is transported to the development module PM6 by the fifth transport device HD5. In the development module PM6, the resist film on the substrate W is developed. The development process may be performed by dry development. The development process in step ST700 may be performed by this processing method (see FIGS. 4 and 13). Desorption processing may be executed one or more times after or during the development process. The desorption process includes removing scum (descum) or smoothing the surface from the surface of the resist film by an inert gas such as helium or plasma of the inert gas. Further, in the development processing module PM6, after the development process, a part of the underlying film may be etched using the developed resist film as a mask.

[0143] (Step ST800: PB) Next, the substrate W is transferred by the fifth transfer device HD5 to the third thermal treatment module PM7, where it is subjected to a heat treatment (post-bake). The post-bake may be performed in an air atmosphere or a reduced-pressure atmosphere containing N2 or O2. The post-bake may be performed by heating the substrate W to a temperature of 150°C or higher and 250°C or lower. The post-bake may be performed in the second thermal treatment module PM4 instead of the third thermal treatment module PM7. In one embodiment, after the post-bake, the measurement modules PM4 and PM5 may perform optical measurements of the substrate W. Such measurements may be performed in addition to or instead of the measurement in step ST600. In one embodiment, the controller CT determines whether or not there are any abnormalities, such as defects, scratches, or foreign matter, in the developed pattern of the substrate W, based on the measured appearance, dimensions, and / or pattern shape of the substrate W. In one embodiment, if the controller CT determines that there is an abnormality, the substrate W may be reworked or discarded without being etched in step ST900. In one embodiment, if it is determined that there is an abnormality in the control unit CT, the opening dimensions of the resist film on the substrate W may be adjusted using a dry coating unit (CVD apparatus, ALD apparatus, etc.).

[0144] (Process ST900: Etching) After step ST800 is performed, the substrate W is transferred by the fifth transfer device HD5 to the sixth transfer device HD6 of the second carrier station CS2, and then transferred by the sixth transfer device HD6 to the second carrier C2 of the second mounting plate ST2. The second carrier C2 is then transferred to a plasma processing system (not shown). The plasma processing system may be, for example, the plasma processing system shown in FIGS. 2 and 3. In the plasma processing system, the undercoat film UF of the substrate W is etched using the developed resist film as a mask. This completes the method MT. When the resist film is developed using a plasma processing device in step ST700, etching may be performed subsequently in a plasma processing chamber of the plasma processing device. Furthermore, if the second processing station PS2 includes a plasma processing module in addition to the developing module PM6, etching may be performed in the plasma processing module. The above-described desorption process may be performed one or more times before or during etching.

[0145] Embodiments of the present disclosure further include the following aspects.

[0146] (Appendix 1) A substrate processing method, comprising: (a) providing a substrate on a substrate support within a chamber, the substrate having an underlying film and a metal-containing resist film formed on the underlying film, the metal-containing resist film having a first exposed area and a second unexposed area; (b) supplying a process gas to the chamber to develop the substrate and selectively remove the second region from the metal-containing resist film; The step (b) is (b1) controlling the temperature of the substrate or the substrate support member to a first temperature and performing development; (b2) controlling the temperature of the substrate or the substrate support part to a second temperature different from the first temperature and performing development, Substrate processing method.

[0147] (Appendix 2) 2. The substrate processing method according to claim 1, wherein the second temperature is higher than the first temperature.

[0148] (Appendix 3) 3. The substrate processing method according to claim 1, wherein in the step (b2), no processing gas is supplied to the chamber, or the flow rate of the processing gas supplied to the chamber is lower than the flow rate of the processing gas supplied to the chamber in the step (b1).

[0149] (Appendix 4) 4. The substrate processing method according to claim 1, wherein the pressure in the chamber in the step (b2) is lower than the pressure in the chamber in the step (b1).

[0150] (Appendix 5) 5. The substrate processing method of claim 1, wherein the step (b) further includes a step of purging the processing gas in the chamber between the step (b1) and the step (b2).

[0151] (Appendix 6) 6. The substrate processing method according to claim 1, wherein in the steps (b1) and (b2), a processing gas is supplied to the chamber at a constant flow rate.

[0152] (Appendix 7) A substrate processing method, comprising: (a) providing a substrate having an underlayer and a metal-containing resist film formed on the underlayer on a substrate support within a chamber, the metal-containing resist film having a first exposed area and a second unexposed area; (b) supplying a process gas to the chamber to develop the substrate, thereby selectively removing either the first region or the second region from the metal-containing resist film; The step (b) is (b1) developing the substrate under first developing conditions; (b2) developing the substrate under second developing conditions different from the first developing conditions, wherein the second developing conditions are different from the first developing conditions in at least one of development parameters including a temperature of the substrate or the substrate support, a pressure in the chamber, a flow rate of the process gas, a type of the process gas, and a residence time of the process gas on the substrate; Substrate processing method.

[0153] (Appendix 8) 8. The substrate processing method of claim 7, wherein in the step (b), the development is performed using plasma generated from a processing gas, and the development parameters further include a power level of a source RF signal for plasma generation supplied to the chamber, and a power or voltage level of a bias signal supplied to the chamber.

[0154] (Appendix 9) the bias signal comprises a bias RF signal or a voltage pulse; 9. The substrate processing method according to claim 8, wherein the development parameters further include at least one of a frequency of the source RF signal, a frequency of the bias RF signal, and a frequency of the voltage pulse.

[0155] (Appendix 10) 10. The substrate processing method according to claim 8, wherein at least one of the source RF signal and the bias RF signal is pulsed, and the development parameters further include at least one of a duty ratio of the pulsed source RF signal and a duty ratio of the pulsed bias signal.

[0156] (Appendix 11) 11. The substrate processing method according to claim 7, wherein in the step (b2), the second developing conditions are different from the first developing conditions in two or more of the developing parameters.

[0157] (Appendix 12) A substrate processing method, comprising: 12. The substrate processing method according to any one of claims 1 to 11, wherein in the step (b), the steps (b1) and (b2) are repeated.

[0158] (Appendix 13) 12. The substrate processing method according to any one of Appendix 1 to Appendix 11, wherein in step (b), a cycle including steps (b1) and (b2) is performed one or more times, and then step (b1) is further performed.

[0159] (Appendix 14) 12. The substrate processing method according to any one of Appendix 1 to Appendix 11, wherein the step (b) comprises a step of performing a cycle including the steps (b1) and (b2) one or more times without generating plasma from the processing gas, and then performing a cycle including the steps (b1) and (b2) one or more times with generating plasma from the processing gas.

[0160] (Appendix 15) 12. The substrate processing method according to any one of Appendix 1 to Appendix 11, wherein the step (b) comprises performing a cycle including the steps (b1) and (b2) one or more times by generating plasma from the processing gas, and then performing a cycle including the steps (b1) and (b2) one or more times without generating plasma from the processing gas.

[0161] (Appendix 16) 12. The substrate processing method according to claim 1, wherein in at least one of the steps (b1) and (b2), the first region or the second region is selectively removed using plasma generated from the processing gas.

[0162] (Appendix 17) 17. The substrate processing method according to claim 1, wherein the metal-containing resist film contains at least one metal selected from the group consisting of Sn, Hf, and Ti.

[0163] (Appendix 18) 18. The substrate processing method according to claim 1, wherein the processing gas includes a halogen-containing gas.

[0164] (Appendix 19) 19. The substrate processing method according to any one of claims 1 to 18, wherein the acidity of the processing gas used in the step (b1) is different from the acidity of the processing gas used in the step (b2).

[0165] (Appendix 20) (c) after the step (b), further comprising the step of etching the underlayer film using the developed metal-containing film as a mask.

[0166] (Appendix 21) 21. The substrate processing method according to claim 20, wherein the step (c) is performed in a chamber different from the chamber used in the step (b).

[0167] (Appendix 22) 21. The substrate processing method according to claim 20, wherein the step (c) is performed in the chamber used in the step (b).

[0168] (Appendix 23) 23. The substrate processing method of any one of claims 1 to 22, wherein the first region is exposed to EUV light.

[0169] (Appendix 24) 24. The substrate processing method according to any one of claims 1 to 23, wherein the temperature of the substrate or the substrate support is controlled by at least one selected from the group consisting of output of a heater in the substrate support, output of a heater in a side wall of a chamber accommodating the substrate support, output of a heater in a ceiling of the chamber, temperature of a heat transfer fluid flowing in the substrate support, pressure of a heat transfer gas supplied between the back surface of the substrate and the front surface of the substrate support, and output of an electromagnetic wave configured to be irradiated onto the front surface of the substrate.

[0170] (Appendix 25) A substrate processing system including a substrate processing apparatus having a chamber and a control unit, wherein the control unit controls the substrate processing apparatus to: (a) providing a substrate having an underlayer film and a metal-containing resist film formed on the underlayer film to a substrate support of a chamber, the metal-containing resist film having a first exposed area and a second unexposed area; (b) controlling a process gas to be supplied to the chamber to develop the substrate and selectively remove the second region from the metal-containing resist film; The control of (b) is (b1) controlling the temperature of the substrate or the substrate support member to a first temperature to perform development; (b2) controlling the temperature of the substrate or the substrate support part to a second temperature different from the first temperature to perform development, Substrate processing system.

[0171] (Appendix 26) A substrate processing system including a substrate processing apparatus having a chamber and a control unit, wherein the control unit controls the substrate processing apparatus to: (a) providing a substrate having an underlying film and a metal-containing resist film formed on the underlying film to a substrate support in a chamber, the metal-containing resist film having a first exposed area and a second unexposed area; (b) supplying a process gas to the chamber to develop the substrate and selectively removing either the first region or the second region from the metal-containing resist film; The control of (b) is (b1) controlling development of the substrate under first development conditions; (b2) Control of developing the substrate under second developing conditions different from the first developing conditions, wherein the second developing conditions are different from the first developing conditions in at least one of development parameters including a temperature of the substrate, a pressure in the chamber, a flow rate of the process gas, a type of the process gas, and a residence time of the process gas on the substrate. Substrate processing system.

[0172] (Appendix 27) 1. A device manufacturing method comprising: (a) providing a substrate on a substrate support within a chamber, the substrate having an underlying film and a metal-containing resist film formed on the underlying film, the metal-containing resist film having a first exposed area and a second unexposed area; (b) supplying a process gas to the chamber to develop the substrate and selectively remove the second region from the metal-containing resist film; The step (b) is (b1) controlling the temperature of the substrate or the substrate support member to a first temperature and performing development; (b2) controlling the temperature of the substrate or the substrate support part to a second temperature different from the first temperature and performing development, Device manufacturing methods.

[0173] (Appendix 28) 1. A device manufacturing method comprising: (a) providing a substrate having an underlayer and a metal-containing resist film formed on the underlayer on a substrate support within a chamber, the metal-containing resist film having a first exposed area and a second unexposed area; (b) supplying a process gas to the chamber to develop the substrate, thereby selectively removing either the first region or the second region from the metal-containing resist film; The step (b) is (b1) developing the substrate under first developing conditions; (b2) developing the substrate under second developing conditions different from the first developing conditions, wherein the second developing conditions are different from the first developing conditions in at least one of development parameters including a temperature of the substrate or the substrate support, a pressure in the chamber, a flow rate of the process gas, a type of the process gas, and a residence time of the process gas on the substrate; Device manufacturing methods.

[0174] (Appendix 29) A computer of a substrate processing system having one or more substrate processing apparatuses and a control unit, (a) providing a substrate having an underlayer film and a metal-containing resist film formed on the underlayer film to a substrate support of a chamber, the metal-containing resist film having a first exposed area and a second unexposed area; (b) supplying a process gas to the chamber to develop the substrate and selectively removing the second region from the metal-containing resist film, The control of (b) is (b1) controlling the temperature of the substrate or the substrate support member to a first temperature to perform development; (b2) controlling the temperature of the substrate or the substrate support part to a second temperature different from the first temperature to perform development, program.

[0175] (Appendix 30) A computer of a substrate processing system having one or more substrate processing apparatuses and a control unit, (a) providing a substrate having an underlying film and a metal-containing resist film formed on the underlying film to a substrate support in a chamber, the metal-containing resist film having a first exposed area and a second unexposed area; (b) supplying a processing gas to the chamber to develop the substrate, and selectively removing either the first region or the second region from the metal-containing resist film, The control of (b) is (b1) controlling development of the substrate under first development conditions; (b2) Control of developing the substrate under second developing conditions different from the first developing conditions, wherein the second developing conditions are different from the first developing conditions in at least one of development parameters including a temperature of the substrate or the substrate support part, a pressure in the chamber, a flow rate of the processing gas, a type of the processing gas, and a residence time of the processing gas on the substrate. program.

[0176] (Appendix 31) A storage medium storing the program described in Supplementary Note 29 or Supplementary Note 30.

[0177] The above embodiments are described for the purpose of explanation and are not intended to limit the scope of the present disclosure. Various modifications can be made to each embodiment without departing from the scope and spirit of the present disclosure. For example, some components in one embodiment can be added to other embodiments. Also, some components in one embodiment can be replaced with corresponding components in other embodiments. [Explanation of symbols]

[0178] 1: Plasma processing apparatus, 2: Control unit, 10: Plasma processing chamber, 1: Substrate support unit, 20: Gas supply unit, 30: Power supply, 100: Heat processing apparatus, 102: Processing chamber, 120: Stage heater, 121: Substrate support unit, 141: Gas nozzle, 200: Control unit, OP: Opening, RM: Resist film, RM1: First region, RM2: Second region, UF: Undercoat film, W: Substrate

Claims

1. A substrate processing method, comprising: (a) providing a substrate on a substrate support within a chamber, the substrate having an underlying film and a metal-containing resist film formed on the underlying film, the metal-containing resist film having a first exposed area and a second unexposed area; (b) supplying a process gas to the chamber to develop the substrate and selectively remove the second region from the metal-containing resist film; The step (b) (b1) controlling the temperature of the substrate or the substrate support to a first temperature and exposing the substrate to the process gas to perform development; (b2) after the step (b1), controlling the temperature of the substrate or the substrate support member to a second temperature higher than the first temperature, and exposing the substrate to the processing gas to perform development, Substrate processing method.

2. 2. The substrate processing method according to claim 1, wherein in the step (b2), a flow rate of the processing gas supplied to the chamber is smaller than a flow rate of the processing gas supplied to the chamber in the step (b1).

3. 2. The substrate processing method according to claim 1, wherein the pressure in the chamber in the step (b2) is lower than the pressure in the chamber in the step (b1).

4. 2. The substrate processing method according to claim 1, wherein the step (b) further comprises the step of purging the processing gas in the chamber between the step (b1) and the step (b2).

5. 2. The substrate processing method according to claim 1, wherein in the steps (b1) and (b2), a processing gas is supplied to the chamber at a constant flow rate.

6. 2. The substrate processing method according to claim 1, wherein in the step (b), the steps (b1) and (b2) are repeated.

7. 2. The substrate processing method according to claim 1, wherein in the step (b), a cycle including the step (b1) and the step (b2) is performed one or more times, and then the step (b1) is further performed.

8. 2. The substrate processing method of claim 1, wherein the step (b) comprises a step of performing a cycle including the steps (b1) and (b2) one or more times without generating plasma from the processing gas, and then performing a cycle including the steps (b1) and (b2) one or more times by generating plasma from the processing gas.

9. 2. The substrate processing method of claim 1, wherein the step (b) comprises performing a cycle including the steps (b1) and (b2) one or more times by generating plasma from the processing gas, and then performing a cycle including the steps (b1) and (b2) one or more times without generating plasma from the processing gas.

10. 2. The substrate processing method according to claim 1, wherein in at least one of the steps (b1) and (b2), the first region or the second region is selectively removed using plasma generated from the processing gas.

11. 2. The substrate processing method according to claim 1, wherein the metal-containing resist film contains at least one metal selected from the group consisting of Sn, Hf, and Ti.

12. The substrate processing method of claim 1 , wherein the processing gas includes a halogen-containing gas.

13. The halogen-containing gas may be HBr gas, BCl ３ 13. The substrate processing method according to claim 12, wherein the gas comprises at least one selected from the group consisting of a gas, an HCl gas, an HI gas, and an HF gas.

14. 2. The substrate processing method according to claim 1, wherein the processing gas includes a gas containing at least one selected from the group consisting of a carboxylic acid, a β-dicarbonyl compound, and an alcohol.

15. The carboxylic acid-containing gas is formic acid (HCOOH), acetic acid (CH ３ COOH), trichloroacetic acid (CCl ３ COOH), monofluoroacetic acid (CFH ２ COOH), difluoroacetic acid (CF ２ HCOOH), trifluoroacetic acid (CF ３ COOH) chloro-difluoroacetic acid (CClF ２ COOH), sulfur-containing acetic acid, thioacetic acid (CH ３ COSH), thioglycolic acid (HSCH ２ COOH), trifluoroacetic anhydride ((CF ３ CO) ２ O) and acetic anhydride ((CH ３ CO) ２ 15. The substrate processing method according to claim 14, further comprising at least one selected from the group consisting of:

16. The β-dicarbonyl compound is acetylacetone (CH ３ C(O)CH ２ C(O)CH ３ ), trichloroacetylacetone (CCl ３ C(O)CH ２ C(O)CH ３ ), hexachloroacetylacetone (CCl ３ C(O)CH ２ C(O)CCl ３ ), trifluoroacetylacetone CF ３ C(O)CH ２ C(O)CH ３ ) and hexafluoroacetylacetone (HFAc, CF ３ C(O)CH ２ C(O)CF ３ 15. The substrate processing method according to claim 14, wherein the substrate processing step comprises at least one selected from the group consisting of:

17. 2. The substrate processing method according to claim 1, further comprising: (c) after the step (b), a step of etching the underlayer film using the developed metal-containing film as a mask.

18. 18. The substrate processing method according to claim 17, wherein the step (c) is performed in a chamber different from the chamber used in the step (b).

19. 18. The substrate processing method according to claim 17, wherein the step (c) is performed in the chamber used in the step (b).

20. 2. The substrate processing method of claim 1, further comprising the step of: (d) exposing the substrate to plasma generated in the chamber after the step (b).

21. 21. The substrate processing method according to claim 20, wherein the step (d) includes removing scum on the substrate surface or smoothing the surface of the metal-containing resist film.

22. 21. The substrate processing method according to claim 20, wherein the plasma is generated from at least one gas selected from the group consisting of He, Ar, Ne, Kr, Xe, and nitrogen gas.

23. The substrate processing method of claim 1 , wherein the first region is exposed to EUV light.

24. 2. The substrate processing method of claim 1, wherein the temperature of the substrate or the substrate support is controlled by at least one selected from the group consisting of output of a heater in the substrate support, output of a heater in a side wall of a chamber accommodating the substrate support, output of a heater in a ceiling of the chamber, temperature of a heat transfer fluid flowing in the substrate support, pressure of a heat transfer gas supplied between a back surface of the substrate and a front surface of the substrate support, and output of an electromagnetic wave configured to be irradiated onto the front surface of the substrate.

25. A substrate processing system having a substrate processing apparatus and a control unit, The substrate processing apparatus includes a chamber and a gas supply unit that supplies a processing gas into the chamber; a substrate support portion that supports a substrate; a temperature adjusting unit that adjusts the temperature of the substrate or the substrate support unit, The control unit (a) providing a substrate having an underlying film and a metal-containing resist film formed on the underlying film to the substrate support of the chamber, the metal-containing resist film having a first exposed area and a second unexposed area; (b) controlling the gas supply unit to supply a process gas to the chamber to develop the substrate and selectively remove the second region from the metal-containing resist film; The control of (b) is (b1) controlling the temperature of the substrate or the substrate support part to a first temperature by the temperature adjustment part, and performing development by exposing the substrate to the processing gas; (b2) after the control of (b1), controlling the temperature of the substrate or the substrate support part to a second temperature higher than the first temperature by the temperature adjustment part, and exposing the substrate to the processing gas to perform development, Substrate processing system.

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