Substrate processing method and substrate processing system

Abstract

This technology provides a method for suppressing residue in the development pattern. [Solution] A substrate processing method is provided. This method includes (a) a step of providing a substrate having a base film and a metal-containing resist film formed on the base film onto a substrate support in a chamber, wherein the metal-containing resist film has an exposed first region and an unexposed second region; and (b) a step of supplying a processing gas to the chamber to develop the substrate and selectively removing the second region from the metal-containing resist film. Step (b) includes (b1) a step of developing by controlling the temperature of the substrate or substrate support to a first temperature; and (b2) a step of developing by controlling the temperature of the substrate or substrate support to a second temperature different from the first temperature.

Description

Technical Field

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

Background Art

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

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] The present disclosure provides a technique for suppressing residues in a developed pattern.

Means for Solving the Problems

[0005] In one exemplary embodiment of the present disclosure, a substrate processing method includes: (a) providing a substrate having an underlying film and a metal-containing resist film formed on the underlying film on a substrate support in a chamber, the metal-containing resist film having an exposed first region and an unexposed second region; and (b) supplying a processing gas to the chamber to develop the substrate and selectively removing the second region from the metal-containing resist film, the step (b) including: (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. A substrate processing method is provided.

Effects of the Invention

[0006] According to one exemplary embodiment of the present disclosure, a technique for suppressing the residue of the development pattern can be provided. [Brief explanation of the drawing]

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

Modes for Carrying Out the Invention

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

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

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

[0011] In one exemplary embodiment, 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 smaller than the flow rate of the processing gas supplied to the chamber in the step (b1). <s

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

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

[0014] In one exemplary embodiment, in steps (b1) and (b2), a process 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 a base film and a metal-containing resist film formed on the base film to a substrate support in a chamber, wherein the metal-containing resist film has an exposed first region and an unexposed second region; and (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, wherein step (b) comprises (b1) developing the substrate under first development conditions and (b2) developing the substrate under second development conditions different from the first development conditions, wherein at least one of the development parameters, including the temperature of the substrate or substrate support, the pressure in the chamber, the flow rate of the processing gas, the type of processing gas, and the residence time of the processing gas on the substrate, is different from that of the first development conditions.

[0016] In one exemplary embodiment, in step (b), development is performed using plasma generated from the processing gas, and the development parameters further include the power level of the source RF signal for plasma generation supplied to the chamber, and the power or voltage level of the 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 parameter further includes at least one of the frequency of the source RF signal, the frequency of the bias RF signal, and the 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 parameter further includes at least one of the duty cycle of the pulsed source RF signal and the duty cycle 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 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 performed one or more times, and then step (b1) is performed again.

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

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

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

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

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

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

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

[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 the side wall of the chamber housing the substrate support, the output of a heater in the ceiling of the chamber, the temperature of the heat transfer fluid flowing through the substrate support, the pressure of the heat transfer gas supplied between the back surface of the substrate and the surface of the substrate support, and the output of electromagnetic waves configured to irradiate the surface of the substrate.

[0032] In one exemplary embodiment, a substrate processing system is provided having a substrate processing apparatus having a chamber and a control unit, wherein the control unit is configured to perform the following actions on the substrate processing apparatus: (a) providing a substrate having a base film and a metal-containing resist film formed on the base film to a substrate support in the chamber, wherein the metal-containing resist film has an exposed first region and an unexposed second region; and (b) supplying a processing gas to the chamber to develop the substrate and selectively removing the second region from the metal-containing resist film, wherein the control in (b) includes (b1) controlling the temperature of the substrate or substrate support to a first temperature to perform development, and (b2) controlling the temperature of the substrate or substrate support to a second temperature different from the first temperature to perform development.

[0033] Hereinafter, each embodiment of this disclosure will be described in detail with reference to the drawings. In each drawing, the same or similar elements are denoted by the same reference numeral, and redundant explanations are omitted. Unless otherwise specified, positional relationships such as top, bottom, 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 actual ratios are not limited to those shown.

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

[0035] The heat treatment apparatus 100 has a processing chamber 102 configured to form a sealed space. The processing chamber 102 is, for example, an airtight cylindrical container and is configured to allow adjustment of the internal atmosphere. Side wall heaters 104 are provided on the side walls of the processing chamber 102. A ceiling heater 130 is provided on the ceiling wall (top plate) of the processing chamber 102. The 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 section 121 is provided in the lower part of the processing chamber 102. The substrate support section 121 has a substrate support surface on which a substrate W is supported. The substrate support section 121 is, for example, formed in a circular shape in plan view, and the substrate W is placed on its horizontally formed surface (upper surface). A stage heater 120 is embedded in the substrate support section 121. This stage heater 120 can heat the substrate W placed on the substrate support section 121. A ring assembly (not shown) may be arranged in the substrate support section 121 so as to surround the substrate W. The ring assembly may include one or more annular members. By arranging the ring assembly around the substrate W, the temperature controllability of 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] Figure 1B is a plan view showing another example of the substrate support. In one embodiment, the substrate support 121a shown in Figure 1B may be used instead of the substrate support 121 shown in Figure 1A. The substrate support 121a shown in Figure 1B has multiple zones, and each zone is equipped with a heater electrode. In the example shown in Figure 1B, the substrate support 121a has zones Z1 to Z14, and each zone is equipped with a heater electrode. The heater electrode of each zone is configured to be able to receive power independently. That is, the substrate support 121a is configured to be able to control the temperature independently for each zone. Therefore, the substrate support 121a can improve the in-plane uniformity in the development of the resist film RM, which will be described later. Furthermore, the substrate support 121a can be used to sequentially heat the substrate W from the center to the edge, or sequentially heat the substrate W from the edge to the center. In addition, the substrate support 121a can be used to heat a specific area of ​​the substrate W to a higher temperature than other areas.

[0038] The substrate support section 121 is supported within the processing chamber 102 by a support column 122 provided on the bottom surface of the processing chamber 102. Multiple vertically movable lifting pins 123 are provided on the outer circumferential side of the support column 122. Each of the multiple lifting pins 123 is inserted through a through hole provided in the substrate support section 121. The multiple lifting pins 123 are arranged with spacing in the circumferential direction. The lifting and lowering movement of the multiple lifting pins 123 is controlled by a lifting mechanism 124. When the lifting pins 123 protrude from the surface of the substrate support section 121, it becomes possible to transfer the substrate W between the transport mechanism (not shown) and the substrate support section 121.

[0039] An exhaust port 131 with an opening is provided in the side wall of the processing chamber 102. The exhaust port 131 is connected to an exhaust mechanism 132 via an exhaust pipe. The exhaust mechanism 132 consists of a vacuum pump and valves, 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 and other parameters by this exhaust mechanism 132. In addition, a transport port for substrates W (not shown) is formed in the side wall of the processing chamber 102 at a position different from the opening of the exhaust port 131, and is openable and closable.

[0040] Furthermore, a gas nozzle 141 is provided on the side wall of the processing chamber 102 at a position different from the exhaust port 131 and the substrate W transport port. The gas nozzle 141 supplies processing gas into the processing chamber 102. The gas nozzle 141 is located on the side wall of the processing chamber 102, on the opposite side of the exhaust port 131 when viewed from the center of the substrate support portion 121. That is, the gas nozzle 141 is located on the side wall of the processing chamber 102, symmetrically with respect to the exhaust port 131 with respect to a vertical virtual plane passing through the center of the substrate support portion 121.

[0041] The gas nozzle 141 is formed in a rod shape that protrudes from the side wall 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 side wall of the processing chamber 102. The processing gas is discharged into the processing chamber 102 from the discharge port that opens at the tip of the gas nozzle 141, flows in the direction of the dashed arrow shown in Figure 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 also have a shape that extends diagonally downward toward the substrate W, or a shape that extends diagonally upward toward the 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. Multiple gas nozzles 141 may be provided on the ceiling wall. Alternatively, instead of gas nozzles, a configuration similar to the shower head 13 in Figure 3, which will be described later, may be provided. The flow rate and type of gas supplied to the substrate W from multiple gas nozzles or shower heads may be configured to be controllable for each region of the substrate W (for example, zones Z1 to Z14 in Figure 1B). In one embodiment, the flow rate of gas supplied to the central region of the substrate W may be greater than the flow rate of gas supplied to the outer region 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 is provided around the gas supply pipe 152 to heat the gas inside the gas supply pipe. The gas supply pipe 152 is connected to a gas supply unit 170. The gas supply unit 170 includes at least one gas source and at least one flow controller. The gas supply unit may include a vaporizer for vaporizing a material in a liquid state.

[0044] The control unit 200 processes computer-executable instructions that cause the heat treatment apparatus 100 to perform various processes described herein. The control unit 200 may be configured to control each element of the heat treatment apparatus 100 to perform the various processes 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 a computer 200a. The processing unit 200a1 may be configured to perform various control operations by reading a program from the storage unit 200a2 and executing the read program. This program may be stored in the storage unit 200a2 in advance, or it may be retrieved via a medium when needed. The retrieved program is stored in the storage unit 200a2 and read from the storage unit 200a2 and executed by the processing unit 200a1. The medium may be various storage media readable by the computer 200a, or it may be a communication line connected to the communication interface 200a3. The processing unit 200a1 may be a CPU (Central Processing Unit). The storage unit 200a2 may include RAM (Random Access Memory), ROM (Read Only Memory), HDD (Hard Disk Drive), SSD (Solid State Drive), or a combination thereof. The communication interface 200a3 may communicate with the heat treatment apparatus 100 via a communication line such as a LAN (Local Area Network).

[0045] <Example of a plasma processing system configuration> Figure 2 is a diagram illustrating an example configuration when a plasma processing system is used as a developing processing system. In one embodiment, the plasma processing system includes a plasma processing apparatus 1 and a control unit 2. The plasma processing system is an example of a substrate processing system, and the plasma processing apparatus 1 is an example of a substrate processing apparatus. The plasma processing apparatus 1 includes a plasma processing chamber (hereinafter also simply referred to as the "processing chamber") 10, a substrate support section 11, and a plasma generation section 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 outlet for discharging gas from the plasma processing space. The gas supply port is connected to a gas supply section 20, which will be described later, and the gas outlet is connected to an exhaust system 40, which will be described later. The substrate support section 11 is located in the plasma processing space and has a substrate support surface for supporting a substrate.

[0046] The plasma generation 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 a capacitively coupled plasma (CCP), an inductively coupled plasma (ICP), an electron-cyclotron-resonance plasma (ECR), a helicon wave-excited plasma (HWP), or a surface wave plasma (SWP), etc. Various types of plasma generation units, including an AC (Alternating Current) plasma generation unit and a DC (Direct Current) plasma generation unit, may also be used. In one embodiment, the AC signal (AC power) used in the AC plasma generation unit has a frequency in the range of 100 kHz to 10 GHz. Therefore, the AC signal includes an RF (Radio Frequency) signal and a microwave signal. In one embodiment, the RF signal has a frequency in the range of 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 processes described herein. The control unit 2 may be configured to control the elements of the plasma processing apparatus 1 to perform the various processes 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 implemented, for example, by a computer 2a. The control unit 2 may include a processing unit 2a1, a storage unit 2a2, and a communication interface 2a3. Each configuration of the control unit 2 may be the same as each configuration of the control unit 200 (see Figure 1A) described above.

[0048] The following describes an example configuration of a capacitively coupled plasma processing apparatus as an example of plasma processing apparatus 1. Figure 3 is a diagram illustrating an example configuration of a capacitively coupled plasma processing apparatus.

[0049] The capacitively coupled plasma processing apparatus 1 includes a plasma processing chamber 10, a gas supply unit 20, a power supply 30, and an exhaust system 40. The plasma processing apparatus 1 also includes a substrate support unit 11 and a gas introduction unit. The gas introduction unit is configured to introduce at least one processing gas into the plasma processing chamber 10. The gas introduction unit includes a shower head 13. The substrate support unit 11 is located inside the plasma processing chamber 10. The shower head 13 is located above the substrate support unit 11. In one embodiment, the shower head 13 constitutes at least a portion of the ceiling of the plasma processing chamber 10. The plasma processing chamber 10 has a plasma processing space 10s defined by the shower head 13, the side walls 10a of the plasma processing chamber 10, and the substrate support unit 11. The plasma processing chamber 10 is grounded. The shower head 13 and the substrate support unit 11 are electrically insulated from the housing of the plasma processing chamber 10.

[0050] The substrate support portion 11 includes a main body portion 111 and a ring assembly 112. The main body portion 111 has a central region 111a for supporting the substrate W and an annular region 111b for supporting the ring assembly 112. A wafer is an example of the substrate W. The annular region 111b of the main body portion 111 surrounds the central region 111a of the main body portion 111 in a plan view. The substrate W is placed on the central region 111a of the main body portion 111, and the ring assembly 112 is placed on the annular region 111b of the main body portion 111 so as to surround the substrate W on the central region 111a of the main body portion 111. Therefore, the central region 111a is also called the substrate support surface for supporting the substrate W, and the annular region 111b is also called the 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 placed on the base 1110. The electrostatic chuck 1111 includes a ceramic member 1111a and an electrostatic electrode 1111b placed 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. Other members surrounding the electrostatic chuck 1111, such as an annular electrostatic chuck or an annular insulating member, may also have an annular region 111b. In this case, the ring assembly 112 may be placed on the annular electrostatic chuck or the annular insulating member, or on both the electrostatic chuck 1111 and the annular insulating member. Furthermore, at least one RF / DC electrode, coupled to the RF power supply 31 and / or DC power supply 32 described later, may be placed within the ceramic member 1111a. In this case, at least one RF / DC electrode functions as a lower electrode. When a bias RF signal and / or DC signal, described later, is supplied to 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 at least one RF / DC electrode may function as multiple lower electrodes. Also, the electrostatic electrode 1111b may function as a lower electrode. Therefore, the substrate support portion 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 covering ring. The edge rings are formed of a conductive or insulating material, and the covering rings are formed of an insulating material.

[0053] The substrate support section 11 may also include a temperature control 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 control 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 within the base 1110, and one or more heaters are arranged within the ceramic member 1111a of the electrostatic chuck 1111. The substrate support section 11 may also include a heat transfer gas supply section configured to supply heat transfer gas to the gap between the back surface of the substrate W and the central region 111a. The substrate support section 11 may have multiple zones, similar to the substrate support section 121a shown in Figure 1B, and each zone may be equipped with a heater electrode. The heater electrode in each zone may be configured to be able to receive power independently. That is, the substrate support section 11 may be configured to be able to control the temperature independently 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 a plurality of gas inlet ports 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 through the plurality of gas inlet ports 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 side wall 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 processing gas to the shower head 13 from a corresponding gas source 21 via a corresponding flow controller 22. Each flow controller 22 may include, for example, a mass flow controller or a pressure-controlled flow controller. Furthermore, the gas supply unit 20 may include at least one flow modulation device that modulates or pulses the flow rate of at least one processing 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 causes plasma to be formed from at least one processing gas supplied to the plasma processing space 10s. Thus, the RF power supply 31 can function as at least part of the plasma generation unit 12. In addition, by supplying a bias RF signal to at least one lower electrode, a bias potential is generated on the substrate W, and ionic components in the formed plasma can be drawn into the substrate W.

[0057] In one embodiment, the RF power supply 31 includes a first RF generation unit 31a and a second RF generation unit 31b. The first RF generation 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 generation unit 31a may be configured to generate a plurality of source RF signals having different frequencies. One or more generated source RF signals are supplied to at least one lower electrode and / or at least one upper electrode.

[0058] The second RF generation unit 31b is coupled to at least one lower electrode via at least one impedance matching circuit and is 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 generation unit 31b may be configured to generate a plurality of bias RF signals having different frequencies. One or more generated 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 generation unit 32a and a second DC generation unit 32b. In one embodiment, the first DC generation unit 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 at least one lower electrode. In one embodiment, the second DC generation unit 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 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 a combination thereof pulse waveform. In one embodiment, a waveform generation unit for generating a sequence of voltage pulses from the DC signal is connected between the first DC generation unit 32a and at least one lower electrode. Thus, the first DC generation unit 32a and the waveform generation unit constitute a voltage pulse generation unit. When the second DC generation unit 32b and the waveform generation unit constitute a voltage pulse generation unit, the voltage pulse generation unit is connected to at least one upper electrode. The voltage pulses may have positive or negative polarity. The sequence of voltage pulses may also include one or more positive voltage pulses and one or more negative voltage pulses within one period. The first and second DC generation units 32a and 32b may be provided in addition to the RF power supply 31, and the first DC generation unit 32a may be provided in place of the second RF generation unit 31b.

[0061] The exhaust system 40 may be connected to, for example, a gas outlet 10e located 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] <An example of a substrate processing method> Figure 4 is a flowchart of a substrate processing method according to an exemplary embodiment (hereinafter also referred to as "this processing method"). As shown in Figure 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 heat treatment system (see Figure 1A) or a plasma treatment system (see Figures 2 and 3). In the following description, a case in which the control unit 200 controls each part of the heat treatment apparatus 100 to perform this processing method on the substrate W will be described as an example.

[0063] (Step ST11: Provision of substrate) First, in step ST11, the substrate W is placed in the processing chamber 102 of the heat treatment apparatus 100. The substrate W is placed on the substrate support 121 via the lifting pin 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 from among the side wall heater 104, stage heater 120, ceiling heater 130, and 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 placed on the substrate support 121 after the temperature of the substrate support 121 has been adjusted to the set temperature.

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

[0065] As shown in Figure 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 exposed by EUV. The second region RM2 is an unexposed region that has not been exposed by EUV. The film thickness of the first region RM1 may be less than the film thickness of the second region RM2.

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

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

[0068] Figures 6 and 7 show examples of undercoat films UF of the substrate W, respectively. As shown in Figure 6, the undercoat film UF may consist of a first film UF1, a second film UF2, and a third film UF3. As shown in Figure 7, the undercoat film UF may consist 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 film (SiARC), or an organic film. The second film UF2 is, for example, a spin-on-carbon (SOC) film, an amorphous carbon film, or a silicon-containing film. The third film UF3 is, for example, a silicon-containing film. The silicon-containing film is, for example, a silicon oxide film, a silicon nitride film, a silicon oxynitride film, a silicon carbonitride film, a polycrystalline silicon film, or a carbon-containing silicon film. The third film UF3 may consist of multiple types of silicon-containing films stacked together. For example, the third film UF3 may consist of alternatingly stacked silicon oxide films and silicon nitride films. Alternatively, the third film UF3 may consist of alternatingly stacked silicon oxide films and polycrystalline silicon films. Furthermore, the third film UF3 may be a stacked film containing a silicon nitride film, a silicon oxide film, and a polycrystalline silicon film. Also, the third film UF3 may consist of stacked silicon oxide films and silicon carbonitride films. Furthermore, the third film UF3 may be a multilayer film containing 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 photoresist film containing metal is deposited on a substrate film that has undergone adhesion treatment or the like. The film deposition may be carried out by a dry process, a wet process such as solution coating, or both a dry and a wet process. The substrate film may be surface modified before deposition of the photoresist film. After deposition of the photoresist film, the substrate undergoes a heat treatment, i.e., pre-bake (Post Applied Bake: PAB). The substrate after pre-bake may undergo additional heat treatment. The substrate after heat treatment is transported to an exposure apparatus, and the photoresist film is irradiated with EUV light through an exposure mask (reticle). This forms a substrate W having a substrate film UF and a resist film RM having an exposed first region RM1 and an unexposed second region RM2. The first region RM1 is a region corresponding to an opening provided in the exposure mask (reticle). The second region RM2 is a region corresponding to a pattern provided in the exposure mask (reticle). EUV has wavelengths in the range of 10 to 20 nm, for example. EUV may have wavelengths in the range of 11 to 14 nm, and in one example, a wavelength of 13.5 nm. After exposure, the substrate is transported from the exposure apparatus to a heat treatment apparatus under controlled atmosphere and undergoes heat treatment, i.e., post-exposure baking (PEB). Additional heat treatment may be performed on the substrate W after PEB.

[0071] (Step ST12: Substrate development) 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 for developing the substrate at a first temperature, step ST121 for developing the substrate at a second temperature different from the first temperature, and step ST122 for determining whether or not the stop condition is met.

[0072] (Step ST120: Development of the substrate at the first temperature) First, in step ST120, a process gas is supplied into the process chamber 102 via a gas nozzle 141. In one embodiment, the process gas includes a halogen-containing gas. The halogen-containing gas may be a gas containing a halogen-containing inorganic acid, and may be 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. In one example, the halogen-containing inorganic acid gas is at least one 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. The organic acid gas may be, for example, a gas containing at least one selected from the group consisting of carboxylic acids, β-dicarbonyl compounds, and alcohols. In one embodiment, the process gas is a gas containing a carboxylic acid. Examples of carboxylic acids include formic acid (HCOOH), acetic acid (CH3COOH), trichloroacetic acid (CCl3COOH), monofluoroacetic acid (CFH2COOH), difluoroacetic acid (CF2HCOOH), trifluoroacetic acid (CF3COOH), chlorodifluoroacetic acid (CClF2COOH), sulfur-containing acetic acid, thioacetic acid (CH3COSH), thioglycolic acid (HSCH2COOH), trifluoroacetic anhydride ((CF3CO)2O), and acetic anhydride ((CH3CO)2O). In one embodiment, the treatment gas contains a β-dicarbonyl compound. The β-dicarbonyl compound may be, for example, acetylacetone (CH3C(O)CH2C(O)CH3), trichloroacetylacetone (CCl3C(O)CH2C(O)CH3), hexachloroacetylacetone (CCl3C(O)CH2C(O)CCl3), trifluoroacetylacetone (CF3C(O)CH2C(O)CH3), or hexafluoroacetylacetone (HFAc,CF3C(O)CH2C(O)CF3). In one embodiment, the first treatment gas contains an alcohol. The alcohol may be, for example, 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 is 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, CFH2COOH, CF2HCOOH, 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 ratio relative to the first region RM1. The first temperature may be appropriately selected depending on the type of processing gas. For example, when HBr gas is used as the processing gas, the first temperature may be, for example, 10°C to 30°C, or 10°C to 20°C, and in one example, 10°C. Step ST120 may be performed until a given period of time has elapsed, or until the second region RM is removed to a given depth. The given period may be, for example, 0.1 seconds to 300 seconds, or 0.1 seconds to 60 seconds, or 60 seconds to 300 seconds.

[0075] (Step ST121: Development of the substrate at the 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 processing gas. For example, when HBr gas is used as the processing gas, it may be 40°C to 100°C, or 50°C to 100°C, and in one example it may be 60°C.

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

[0077] When a process gas is supplied in step ST121, the type of process gas may be the same as or different from the process gas used 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, in step ST121, a process gas with a larger acid dissociation constant (pKa) than the process gas used in step ST120 may be used. 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). Also, in step ST121, the flow rate (partial pressure) of the process gas with a larger acid dissociation constant (pKa) may be increased compared to the flow rate (partial pressure) of the process gas used in step ST120. For example, if the process gas in steps ST120 and ST121 is a mixed gas of HBr gas and carboxylic acid gas, the flow rate (partial pressure) of the carboxylic acid gas may be increased in step ST121.

[0078] In step ST121, the pressure inside the processing chamber 102 may be the same as or different from that in step ST120. In one embodiment, the pressure inside the processing chamber 102 in step ST121 is lower than the pressure inside the processing chamber 102 in step ST120. For example, the pressure inside the processing chamber 102 in step ST120 may be 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 inside the processing chamber 10 in step ST121 may be 0.1 mTorr or more and 100 mTorr or less, or 50 mTorr or more and 100 mTorr or less.

[0079] Process ST121 may be executed 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 a given depth second region RM has been removed.

[0080] (Process ST122: Judgment) In step ST122, it is determined whether a given condition for terminating step ST12 has been met. If it is determined that the given condition has not been met in step ST122, the process returns to step ST120; if it is determined that the given condition has been met, step ST12 is terminated. The given condition may be, for example, that the 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 also be, for example, a condition relating to the development time, i.e., the time elapsed since the start of step ST12. The given condition may also be, for example, a condition relating to the dimensions of the openings or recesses formed in the resist film RM after step ST121, such as the depth or aspect ratio. In this case, after step ST121, it is determined whether the dimensions of the resist film RM have reached a given value or range, and the cycle of steps ST120 and ST121 may be repeated until the dimensions reach that given value or range. The dimensions of the resist film RM may be measured using an optical measuring device.

[0081] In one embodiment, after a cycle including steps ST120 and ST121 has been performed once or more times, a determination may be made not only after the completion of step ST121 but also after the completion of step ST120 to determine whether the given conditions are met. If it is determined that the given conditions are met, step ST12 may be terminated without executing step ST121.

[0082] In one embodiment, a step of purging the gas in the processing chamber 102 from the exhaust port 131 (hereinafter also referred to as the "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 and excess processing gases.

[0083] Figure 8 shows an example of the cross-sectional structure of the substrate W after processing in step ST12. In the example shown in Figure 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 undercoat UF surrounded by the side surface. In a plan view of the substrate W, the opening OP has a shape corresponding to the second region RM2 (and consequently, a shape corresponding to the exposure mask pattern used for EUV exposure). This shape may be, for example, a circle, an ellipse, a rectangle, a line, or a combination of one or more of these. Multiple openings OP may be formed in the resist film RM. Each of the multiple openings OP may have a linear shape and may be arranged at regular intervals to form a line-and-space pattern. Alternatively, multiple openings OP may be arranged in a grid to form a pillar pattern.

[0084] According to this processing method, the temperature of the substrate W or the substrate support portion 121 is changed in steps ST120 and ST121. This makes it possible to adjust the amount of reaction products that volatilize during development. As a result, it is possible to suppress the decrease in development speed due to the inability of reaction products to volatilize, and the formation of residue after development.

[0085] Figure 9 is a diagram illustrating an example of process ST12. In Figure 9, the horizontal axis represents time. The vertical axis represents the flow rate of the processing gas supplied to the processing chamber 102 [sccm], the pressure inside the processing chamber 102 [Torr], and the temperature of the substrate support part 121 [°C]. "Q1" for the processing gas flow rate indicates that no processing gas is being supplied or that the flow rate is lower than that shown by "Q2". "P1" for the pressure inside the processing chamber 102 indicates that the pressure is lower than that shown by "P2". "T1" for the temperature of the substrate support part 121 indicates that the temperature is lower than that shown by "T2". "T1" corresponds to the first temperature, and "T2" corresponds to the second temperature. Figure 9 is an example of a case in process ST12 where the temperature of the substrate support part 121 is alternately changed between "T1" (process ST120) and "T2" (process ST121) while keeping the flow rate of the processing gas and the pressure inside the processing chamber 102 constant.

[0086] Figure 10 schematically shows an example of a phenomenon occurring on the surface of the substrate W in the example shown in Figure 9. In step ST120, the reaction product R generated by the reaction between the resist film in the second region RM2 and the processing gas volatilizes, and the second region RM2 is removed. As development progresses and the depressions formed in the resist film RM become deeper, the reaction product R may accumulate in the depressions, increasing the internal pressure and suppressing the volatilization of the reaction product R. In this regard, in the example shown in Figure 9, in step ST121, development is performed at a higher temperature (T2>T1) for the substrate support portion 121 than in step ST120. Therefore, as shown in Figure 10, the volatilization of the reaction product R is accelerated compared to step ST120. This can suppress the accumulation of the reaction product R in the depressions and the resulting decrease in the development rate.

[0087] If development continues at high temperatures, the development speed of the first region RM1 increases, and it may be removed along with the second region RM2. In this respect, in the example shown in Figure 9, the development at low temperature (T1) in step ST120 and the development at high temperature (T2) in step ST121 are repeated alternately, so that development at high temperature (T2) continues. This can suppress the excessive removal of the first region RM1 and the resulting decrease in film thickness. In other words, the development selectivity (the ratio of the development speed of the second region RM2 to the development speed of the first region RM1, also called the development contrast) is improved.

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

[0089] In the example shown in Figure 11, similar to the example shown in Figure 9, development is performed in step ST121 at a higher temperature (T2>T1) than in step ST120. Therefore, the volatilization of the reaction product R is accelerated compared to step ST120. This can suppress the accumulation of the reaction product R in the recesses, which can reduce the development speed. Also in the example shown in Figure 11, similar to the example shown in Figure 9, development at a low temperature (T1) in step ST120 and development at a high temperature (T2) in step ST121 are repeated alternately, thus avoiding prolonged development at a high temperature (T2). Furthermore, in the example shown in Figure 11, during development at a high temperature (T2) in step ST121, the amount of processing gas supplied is reduced compared to step ST120 or becomes zero. This can mitigate the increase in the development speed of the first region RM1 due to the temperature rise of the substrate support 121. As a result, excessive removal of the first region RM1 and a reduction in film thickness can be suppressed. In other words, the development selectivity (the ratio of the development speed in the second region RM2 to the development speed in the first region RM1, also known as the development contrast) is improved.

[0090] In the example shown in Figure 11, the timing of the increase (decrease) in the flow rate of the processing gas and the decrease (increase) in the temperature of the substrate support part coincide. However, the timings of each may be entirely or partially different (they may be out of phase). In other words, in process ST121, it is sufficient that at least a portion of 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.

[0091] Figure 12 is a diagram illustrating an example of process ST12. The vertical and horizontal axes of Figure 12 are the same as in Figure 9. The example shown in Figure 12 differs from the example shown in Figure 11 in that it includes a purging process between process ST120 and process ST121, and in process ST121, the pressure (P1) inside the processing chamber 102 is lower than the pressure (P2) in process ST120.

[0092] In the example shown in Figure 12, similar to the example shown in Figure 9, development is performed in step ST121 at a higher temperature (T2>T1) than in step ST120 for the substrate support portion 121. Therefore, the volatilization of the reaction product R is accelerated compared to step ST120. In addition, in the example shown in Figure 12, a purging step is performed between steps ST120 and ST121. This can suppress the accumulation of the reaction product R in the recesses, which can reduce the development speed. Also, in the example shown in Figure 12, similar to the example shown in Figure 9, development at a low temperature (T1) in step ST120 and development at a high temperature (T2) in step ST121 are repeated alternately, thus avoiding prolonged development at a high temperature (T2). Furthermore, in the example shown in Figure 12, during development at a high temperature (T2) in step ST121, the amount of processing gas supplied is reduced compared to step ST120 or becomes zero, and the pressure inside the processing chamber 102 is lower than in step ST120. This can mitigate the increase in the development speed of the first region RM1 due to the temperature rise of the substrate support 121. As a result, excessive removal of the first region RM1 and a reduction in film thickness can be suppressed. In the example shown in Figure 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 coincide, but each timing may be entirely or partially different (they may be out of phase). That is, in step ST121, it is sufficient that at least a portion of the period during which the flow rate of the processing gas is Q1 and the period during which the temperature of the substrate support is T2 overlap.

[0093] In one embodiment, the processing method may be performed using a plasma processing system (see Figures 2 and 3). For example, a substrate W may be placed on a substrate support 11 in the processing chamber 10 of the plasma processing apparatus 1 (step ST11), and the resist film RM may be developed by adjusting the temperature of the substrate W or the substrate support 11 with a temperature control module (step ST12). The temperature of the substrate W or the substrate support 11 may be adjusted by controlling the pressure of the heat transfer gas (e.g., He) between the electrostatic chuck 1111 and the back surface of the substrate W. The processing gas used in step ST12 may be the same as when a heat processing system is used. In steps ST120 and / or 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 developing process in step ST12 may be performed by both heat treatment and plasma treatment. For example, one or more cycles in which steps ST120 and ST121 are performed by heat treatment (hereinafter also referred to as the "heat treatment cycle") may be performed, followed by one or more cycles in which steps ST120 and ST121 are performed by plasma treatment (hereinafter also referred to as the "plasma treatment cycle"). Alternatively, one or more plasma treatment cycles may be performed, followed by one or more heat treatment cycles. Alternatively, heat treatment cycles and plasma treatment cycles may be performed alternately multiple times. Alternatively, 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, instead of adjusting the temperature of the substrate support portion (substrate support portion 121 or substrate support portion 11) in step ST12, the temperature of the substrate W in step ST121 may be made different from the temperature of the substrate W in step ST120 by directly heating the substrate W. 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 includes removing scum from the surface of the resist film RM and the surface of the undercoat film UF, or smoothing the surface of the resist film RM, using an inert gas or a 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 development 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 heat processing apparatus 100. The inert gas is, in one example, a noble gas such as He, Ar, Ne, Kr, Xe, or nitrogen gas.

[0097] In one embodiment, the processing method may include a step of etching the underlayer film UF after step ST12. Etching may be performed, for example, by generating plasma from a processing gas in the processing chamber 10 of the plasma processing apparatus 1. In etching, the resist film RM functions as a mask, and recesses are formed in the underlayer film UF based on the shape of the opening OP. When development is performed using the plasma processing apparatus 1 in step ST12, the etching process may be performed continuously in the same processing chamber 10 as in step ST12, or it may be performed in the processing chamber 10 of a different plasma processing apparatus 1.

[0098] Figure 13 is a flowchart showing a modified version of the processing method. As shown in Figure 13, step ST12 may include step ST120A, which develops the substrate under first developing conditions, and step ST121A, which develops the substrate under second developing conditions, instead of steps ST120 and ST121 described above. This modified version may be performed in a heat treatment system (see Figure 1A) or a plasma treatment system (see Figures 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 in 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 processing chamber (102, 10), the flow rate of the processing gas, the type of processing gas, and the residence time. The residence time is the residence time of the processing gas on the substrate W. The residence time is expressed as (P × V) / Q, where V is the volume of the processing chamber, P is the pressure in the processing chamber, and Q is the flow rate of the processing gas. When this processing method is performed using a plasma processing system (see Figures 2 and 3), the development parameters may further include the power level of the source RF signal for plasma generation supplied to the processing chamber 10, and the power or voltage level of the bias signal supplied to the processing chamber 10. The development parameters may further include the frequency of the source RF signal. If the source RF signal is pulsed, the development parameters may further include the duty cycle 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 cycle of the pulsed bias RF signal. If the bias signal includes voltage pulses, the development parameters may further include the frequency (pulse frequency) and duty cycle of the voltage pulses.

[0100] Figure 14 is a diagram illustrating an example of process ST12 in a modified example. In Figure 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] inside the processing chamber (102, 10). "Q1" for the processing gas flow rate indicates that no processing gas is supplied or that it is less than the flow rate shown in "Q2". "P1" for the pressure inside the processing chamber 102 indicates that the pressure is lower than "P2". Figure 14 is an example where two of the development parameters, the processing gas flow rate and the pressure inside the processing chamber, are different between the first and second development conditions. The remaining development parameters may be the same for development condition 1 and development condition 2. In the example shown in Figure 14, the timing of the increase (decrease) in the processing gas flow rate and the decrease (increase) in the pressure inside the chamber coincide, but the timing of each may be all or part different (the phase may be shifted). In other words, in process ST121A, it is sufficient that at least a portion of the period during which the flow rate of the processing gas is Q1 and the period during which the pressure inside the chamber is P2 overlap.

[0101] Figure 15 is a diagram illustrating an example of step ST12 in a modified example. In Figure 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 treatment chamber (102, 10). "Q1" for the flow rate of the first gas 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". "Q3" for the flow rate of the second gas 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". Figure 15 is an example of the development parameters of the first and second development conditions when the type of processing gas is different. In one embodiment, the second gas is a gas with a larger acid dissociation constant (pKa) than the first gas. In this case, the acidity of the processing gas used in step ST121A is less than the acidity of the processing gas used in step ST120A. Furthermore, the remaining development parameters may be the same for development condition 1 and development condition 2. Also, in the example shown in Figure 15, the timing of the increase (decrease) in the flow rate of the first processing gas and the decrease (increase) in the flow rate of the second processing gas coincide, but the timings of each may be entirely or partially different (they may be out of phase). In other words, in process ST121, it is sufficient that at least a portion of the period when the flow rate of the first gas is Q1 and the period when the flow rate of the second gas is Q4 overlap.

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

[0103] <Examples> Next, examples of this processing method will be described. This disclosure is not limited in any way by the following examples.

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

[0105] In step ST11, the substrate W was placed on the substrate support portion 11 in the 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 EUV exposed and a second region RM2 that was not EUV exposed. The underlayer film UF of the substrate W was a silicon oxide film. The film thickness of the second region RM2 was approximately 1.3 times greater than the film thickness of the first region RM1.

[0106] Process ST12 included process ST120, a purging process, and process ST122. In process ST12, no source RF signal or bias signal was supplied. In other words, no plasma was generated from the processing gas in process ST12.

[0107] Process ST120 was performed for 60 seconds. During process ST120, the substrate support section 11 was adjusted to 10°C. The processing gas contained HBr gas and Ar gas. The pressure inside the processing chamber 10 was maintained at 200 mTorr.

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

[0109] Process ST121 was performed for 60 seconds. During process ST121, the substrate support section 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 Figure 5) was developed using the plasma processing apparatus 1 (see Figure 3). The development was performed continuously under the same conditions as step ST120 in Example 1 (temperature of the substrate support section 11: 10°C, pressure of the processing chamber 10: 200 mTorr, and processing gas containing HBr gas and Ar gas). In other words, unlike Example 1, the purging step and step ST121 were not performed in Reference Example 1.

[0111] Figure 16 shows the development results for Example 1 and Reference Example 1. In Figure 16, the horizontal axis "t [sec]" represents the development time [seconds], and the vertical axis "D [au]" represents the normalized film thickness of the resist film RM (ratio to the reference thickness). E1(RM1) shows the result for the first region RM1 of Example 1, and E1(RM2) shows the result for the second region RM2 of Example 1. R1(RM1) shows the result for the first region RM1 of Reference Example 1, and R1(RM2) shows the result for the second region RM2 of Reference Example 1.

[0112] As shown in Figure 16, in Example 1, the second region RM2 was selectively removed by process ST120 (0-60 seconds), purging process (60-90 seconds), process ST121 (90-150 seconds), and a second process ST120 (150-180 seconds). The reduction in film thickness of the first region RM1 was limited, and development contrast was maintained. In contrast, in Reference Example 1, the development speed of the second region RM2 decreased as the development time progressed, and development contrast with the first region RM1 was lost, making it impossible to selectively remove the second region RM2. In Example 1, it is thought that the inclusion of a purging process and the increase in the temperature of the substrate support part 11 in process ST121 suppressed the retention of reaction products in the recesses during development, thereby promoting the development of the second region RM2. Also in Example 1, the processing gas in process ST121 did not contain HBr gas, and the pressure in the processing chamber 10 was maintained lower than in process ST120. This is thought to mitigate the effect of increased development speed due to temperature rise in the substrate support section 11, thereby suppressing the removal of the first region RM1.

[0113] <Example of a PCB processing system configuration> Figure 17 is a block diagram illustrating an example configuration of a substrate processing system SS according to an exemplary embodiment. The substrate processing system SS comprises 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 control unit CT.

[0114] The first carrier station CS1 loads and unloads the first carrier C1 between the first carrier station CS1 and an external system of the substrate processing system SS. The first carrier station CS1 has a mounting platform that includes a plurality of first mounting plates ST1. A first carrier C1 is placed on each first mounting plate ST1, either containing a plurality of substrates W or empty. The first carrier C1 has a housing capable of housing a plurality of substrates W inside. In one example, the first carrier C1 is a FOUP (Front Opening Unified Pod).

[0115] Furthermore, the first carrier station CS1 transports the substrate W between the first carrier C1 and the first processing station PS1. The first carrier station CS1 further comprises a first transport device HD1. The first transport device HD1 is positioned in the first carrier station CS1 between the mounting table and the first processing station PS1. The first transport device HD1 transports and transfers 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 comprise a load lock module. The load lock module may be provided between the first carrier station CS1 and the first processing station PS1. The load lock module can switch its internal pressure between atmospheric pressure and vacuum. "Atmospheric pressure" may be the internal pressure of the first transport device HD1. "Vacuum" is a pressure lower than atmospheric pressure, and may be a moderate vacuum of, for example, 0.1 Pa to 100 Pa. The interior of the second transport device HD2 can be at atmospheric pressure or under vacuum. The load lock module may, for example, transport the substrate W from the first transport device HD1, which is at atmospheric pressure, to the second transport device HD2, which is under vacuum, and also transport the substrate W from the second transport device HD2, which is under 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 comprises a pre-processing module PM1, a resist film formation module PM2, and a first heat treatment module PM3 (hereinafter collectively referred to as the "first substrate processing module PMa"). The first processing station PS1 also has a second transport device HD2 for transporting the substrate W. The second transport device HD2 transports and transfers 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 control unit for adjusting the temperature of the substrate W, a high-precision temperature control unit for adjusting the temperature of the substrate W with high precision, etc. In one embodiment, the pre-treatment module PM1 includes a surface modification treatment unit for performing surface modification treatment on the substrate W. Each treatment unit of the pre-treatment module PM1 may be configured to include a heat treatment device 100 (see Figure 1A), a plasma treatment device 1 (see Figures 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 vapor deposition. In one example, the dry coating unit includes a CVD apparatus or ALD apparatus for chemically depositing the resist film onto the substrate W placed in a chamber, or a PVD apparatus for physically depositing the resist film. The dry coating unit may also be a heat treatment apparatus 100 (see Figure 1) or a plasma treatment apparatus 1 (see Figures 2 and 3).

[0119] In one embodiment, the resist film formation module PM2 includes a wet coating unit. The wet coating unit forms a resist film on the substrate W using a wet process such as liquid-phase deposition. The wet coating unit may, in one example, be 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] In the first heat treatment module PM3, the substrate W is subjected to heat treatment. In one embodiment, the first heat treatment module PM3 includes one or more of the following: a pre-bake (PAB) unit that performs heat treatment on the substrate W on which a resist film is formed; a temperature control unit that adjusts the temperature of the substrate W; and a high-precision temperature control unit that adjusts the temperature of the substrate W with high precision. Each of these units may have one or more heat treatment devices. In one example, the multiple heat treatment devices may be stacked. The heat treatment device may be, for example, a heat treatment device 100 (see Figure 1A). Each heat treatment may be performed at a predetermined temperature using a predetermined gas.

[0122] The first interface station IS1 has a third transport device HD3. The third transport device HD3 transports and transfers the substrate W between the first processing station PS1 and the exposure device EX. The third transport device HD3 has a housing for housing the substrate W, and the temperature, humidity, pressure, etc. inside the housing may be configured to be controllable.

[0123] The exposure apparatus EX exposes the resist film on the substrate W using an exposure mask (reticle). 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 transport device HD4. The fourth transport device HD4 transports and transfers substrates W between the exposure device EX and the second processing station PS2. The fourth transport device HD4 has a housing for housing the substrates W, and the temperature, humidity, pressure, etc. inside the housing may be configured to be controllable.

[0125] The second processing station PS2 performs various processes on the substrate W. In one embodiment, the second processing station PS2 comprises a second heat treatment module PM4, a measurement module PM5, a developing module PM6, and a third heat treatment module PM7 (hereinafter collectively referred to as the "second substrate processing module PMb"). The second processing station PS2 also has a fifth transport device HD5 for transporting the substrate W. The fifth transport device HD5 transports and transfers the substrate W between two designated second substrate processing modules PMb, and between the second processing station PS2 and the second carrier station CS2 or the second interface station IS2.

[0126] In the second heat treatment module PM4, the substrate W is subjected to heat treatment. In one embodiment, the heat treatment module PM4 includes one or more of the following: a post-exposure bake (PEB) unit for heat treatment of the substrate W after exposure, a temperature control unit for adjusting the temperature of the substrate W, and a high-precision temperature control unit for adjusting the temperature of the substrate W with high precision. Each of these units may have one or more heat treatment devices. In one example, the multiple heat treatment devices may be stacked. The heat treatment device may be, for example, a heat treatment device 100 (see Figure 1A). Each heat 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 a mounting stage on which the substrate W is placed, an imaging device, an illumination device, and an imaging unit including various sensors (temperature sensor, reflectance measuring sensor, etc.). The imaging device may be, for example, a CCD camera that images the appearance of the substrate W. Alternatively, the imaging device may be a hyperspectral camera that spectrally separates light into wavelengths and takes images. 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 developing on the substrate W. The dry developing unit may be, for example, a heat treatment apparatus 100 (see Figure 1A) or a plasma treatment apparatus 1 (see Figures 2 and 3).

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

[0130] The second carrier station CS2 loads and unloads the second carrier C2 between the second carrier station CS2 and an external system of the substrate processing system SS. The configuration and functions of the second carrier station CS2 may be the same as those of the first carrier station CS1 described above.

[0131] The control unit CT controls each component of the substrate processing system SS to execute a given process on the substrate W. The control unit CT stores a recipe that sets the process procedure, process conditions, transport conditions, etc., and controls each component of the substrate processing system SS to execute a given process on the substrate W according to the recipe. The control unit CT may also perform some or all of the functions of each control unit (control units 200 and 2, and 400 shown in Figures 1A to 4).

[0132] <An example of a substrate processing method> Figure 18 is a flowchart illustrating a substrate processing method according to an exemplary embodiment (hereinafter also referred to as "Method MT"). As shown in Figure 18, Method MT includes a step ST100 of pre-treating the substrate, a step ST200 of forming a resist film on the substrate, a step ST300 of applying a heat treatment (pre-bake: PAB) to the substrate on which the resist film has been formed, a step ST400 of performing EUV exposure on the substrate, a step ST500 of applying a heat treatment (post-exposure bake: PEB) to the substrate after exposure, a step ST600 of measuring the substrate, a step ST700 of developing the resist film on the substrate, a step ST800 of applying a heat treatment (post-bake: PB) to the substrate after development, and a step ST900 of etching the substrate. Method MT does not have to include one or more of the above steps. For example, Method MT does not have to include step ST600, and step ST700 may be performed after step ST500.

[0133] Method MT may be performed using the substrate processing system SS shown in Figure 17. Below, we will explain the case in which the control unit CT of the substrate processing system SS controls each part of the substrate processing system SS to perform Method MT on the substrate W as an example.

[0134] (Process ST100: Pre-treatment) First, a first carrier C1 containing multiple substrates W is brought into the first carrier station CS1 of the substrate processing system SS. The first carrier C1 is placed on the first mounting plate ST1. Next, each substrate W in the first carrier C1 is sequentially removed by the first transport device HD1 and transferred to the second transport device HD2 of the first processing station PS1. The substrates W are then transported to the pre-processing module PM1 by the second transport device HD2. The pre-processing module PM1 performs pre-processing on the substrates W. The pre-processing may include, for example, one or more of the following: temperature adjustment of the substrates W, formation of part or all of the undercoat of the substrates W, heat treatment of the substrates W, and high-precision temperature adjustment of the substrates W. The pre-processing may also include surface modification treatment of the substrates W.

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

[0136] The resist film on the substrate W may be formed using both a dry process and a wet process. For example, a first resist film may be formed on the substrate W by a dry process, and then 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 and second resist films may be the same or different.

[0137] (Process ST300:PAB) Next, the substrate W is transported to the first heat treatment module PM3 by the second transport device HD2. The substrate W is subjected to heat treatment (pre-bake: PAB) by the first heat treatment module PM3. Pre-bake may be performed in an air atmosphere or in an inert atmosphere. Pre-bake may also 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 or 250°C or lower. When a resist film is formed by a dry process in step ST200, in one embodiment, pre-bake may be performed continuously in the dry coating unit that performed step ST200. In one embodiment, after pre-bake, an edge bead removal (EBR) may be performed to remove the resist film from the edges of the substrate W.

[0138] (Process ST400: EUV exposure) Next, the substrate W is transferred by the second transport device HD2 to the third transport device HD3 of the first interface station IS1. Then, the substrate W is transported by the third transport device HD3 to the exposure device EX. In the exposure device EX, the substrate W undergoes EUV exposure via an exposure mask (reticle). As a result, the substrate W is divided into a first region that has been EUV exposed and a second region that has not been EUV exposed, corresponding to the pattern of the exposure mask (reticle).

[0139] (Process ST500:PEB) Next, the substrate W is transferred from the fourth transport device HD4 of the second interface station IS2 to the fifth transport device HD5 of the second processing station PS2. The substrate W is then transported by the fifth transport device HD5 to the second heat treatment module PM4. In the second heat treatment module PM4, the substrate W is subjected to heat treatment (post-exposure bake: PEB). The post-exposure bake may be performed in an air atmosphere. Alternatively, the post-exposure bake may be performed by heating the substrate W to a temperature between 180°C and 250°C.

[0140] (Process ST600: Measurement) Next, the substrate W is transported to the measurement module PM5 by the fifth transport device HD5. The measurement module PM5 measures the substrate W. The measurement may be an optical measurement or another method. In one embodiment, the measurement by the measurement module PM5 includes measuring the appearance and / or dimensions of the substrate W using a CCD camera. In one embodiment, the measurement by the measurement module PM5 includes measuring 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 whether or not there is an exposure abnormality in the substrate W based on the measured appearance, dimensions, and / or pattern shape of the substrate W. In one embodiment, if the control unit CT determines that there is an exposure abnormality, the substrate W may be reworked or discarded without performing development in step ST700. Reworking the substrate W may be performed by removing the resist on the substrate W and returning to step ST200 to form a resist film again. Reworking after development may cause damage to the substrate W, but by performing rework before development, damage to the substrate W can be avoided or suppressed.

[0142] (Process ST700: Development) Next, the substrate W is transported to the developing module PM6 by the fifth transport device HD5. In the developing 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 Figures 4 and 13). After or during the development process, a desorption process may be performed one or more times. The desorption process includes removing scum from the surface of the resist film or smoothing the surface using an inert gas such as helium or a plasma of the inert gas. In addition, in the developing module PM6, after the development process, a portion of the underlying film may be etched using the developed resist film as a mask.

[0143] (Process ST800:PB) Next, the substrate W is transported to the third heat treatment module PM7 by the fifth transport device HD5 and subjected to heat treatment (post-bake). Post-bake may be performed in an air atmosphere or in a reduced pressure atmosphere containing N2 or O2. Post-bake may also be performed by heating the substrate W to a temperature of 150°C or higher and 250°C or lower. Post-bake may be performed in the second heat treatment module PM4 instead of the third heat treatment module PM7. In one embodiment, after post-bake, optical measurement of the substrate W may be performed by the measurement modules PM4 and PM5. Such measurement may be performed in addition to or instead of the measurement in process ST600. In one embodiment, the control unit CT determines whether there are any abnormalities such as defects, scratches, or foreign matter adhesion 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 control unit CT determines that there is an abnormality, the substrate W may be reworked or discarded without performing etching in process ST900. In one embodiment, if the control unit CT determines that there is an abnormality, the aperture size 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 completed, the substrate W is transferred by the fifth transport device HD5 to the sixth transport device HD6 of the second carrier station CS2, and then transported by the sixth transport device HD6 to the second carrier C2 of the second mounting plate ST2. Subsequently, the second carrier C2 is transported to a plasma processing system (not shown). The plasma processing system may be, for example, the plasma processing system shown in Figures 2 and 3. In the plasma processing system, the underlayer film UF of the substrate W is etched using the developed resist film as a mask. This completes method MT. Note that if the resist film is developed using a plasma processing apparatus in step ST700, etching may be performed continuously within the plasma processing chamber of the plasma processing apparatus. Also, if the second processing station PS2 is equipped with a plasma processing module in addition to the development module PM6, etching may be performed within the plasma processing module. The above-described desorption process may be performed one or more times before or during etching.

[0145] Embodiments of this disclosure further include the following aspects:

[0146] (Note 1) A substrate processing method, (a) A step of providing a substrate having a base film and a metal-containing resist film formed on the base film onto a substrate support portion in a chamber, wherein the metal-containing resist film has an exposed first region and an unexposed second region, (b) A step of supplying a processing gas to the chamber to develop the substrate and selectively removing the second region from the metal-containing resist film, The above step (b) is: (b1) A step of developing by controlling the temperature of the substrate or the substrate support to a first temperature, (b) A step of developing by controlling the temperature of the substrate or the substrate support to a second temperature different from the first temperature, Substrate processing method.

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

[0148] (Note 3) The substrate processing method according to Appendix 1 or Appendix 2, wherein in step (b2), no processing gas is supplied to the chamber, or the flow rate of the processing gas supplied to the chamber is smaller than the flow rate of the processing gas supplied to the chamber in step (b1).

[0149] (Note 4) The substrate processing method according to any one of Appendix 1 to Appendix 3, wherein the pressure in the chamber during step (b2) is lower than the pressure in the chamber during step (b1).

[0150] (Note 5) The substrate processing method according to any one of Appendix 1 to Appendix 4, wherein step (b) further includes a step of purging the processing gas in the chamber between step (b1) and step (b2).

[0151] (Note 6) The substrate processing method according to any one of Appendix 1 to Appendix 5, wherein in steps (b1) and (b2), a processing gas is supplied to the chamber at a constant flow rate.

[0152] (Note 7) A substrate processing method, (a) A step of providing a substrate having a base film and a metal-containing resist film formed on the base film to a substrate support in a chamber, wherein the metal-containing resist film has an exposed first region and an unexposed second region, (b) A step of 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 above step (b) is: (b1) A step of developing the substrate under first developing conditions, (b2) A step of developing the substrate under second developing conditions different from the first developing conditions, wherein at least one of the developing parameters, including the temperature of the substrate or the substrate support, the pressure in the chamber, the flow rate of the processing gas, the type of the processing gas, and the residence time of the processing gas on the substrate, is different from that of the first developing conditions. Substrate processing method.

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

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

[0155] (Note 10) The substrate processing method according to Appendix 8 or 9, wherein at least one of the source RF signal and the bias RF signal is pulsed, and the development parameter further includes at least one of the duty cycle of the pulsed source RF signal and the duty cycle of the pulsed bias signal.

[0156] (Note 11) In step (b2) above, the substrate processing method according to any one of Appendix 7 to Appendix 10, wherein two or more of the development parameters differ from those of the first development conditions.

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

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

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

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

[0161] (Note 16) A substrate processing method according to any one of Appendix 1 to Appendix 11, 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] (Note 17) The substrate processing method according to any one of Appendix 1 to Appendix 16, wherein the metal-containing resist film comprises at least one metal selected from the group consisting of Sn, Hf, and Ti.

[0163] (Note 18) The substrate processing method according to any one of Appendix 1 to Appendix 17, wherein the processing gas includes a halogen-containing gas.

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

[0165] (Note 20) (c) A substrate processing method according to any one of Appendix 1 to Appendix 19, further comprising the step of etching the underlayer film using the developed metal-containing film as a mask after the step of (b).

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

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

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

[0169] (Note 24) The substrate processing method according to any one of the appendices 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 the output of a heater in the substrate support, the output of a heater in the side wall of the chamber housing the substrate support, the output of a heater in the ceiling of the chamber, the temperature of the heat transfer fluid flowing in the substrate support, the pressure of the heat transfer gas supplied between the back surface of the substrate and the surface of the substrate support, and the output of electromagnetic waves configured to irradiate the surface of the substrate.

[0170] (Note 25) A substrate processing system comprising a substrate processing apparatus having a chamber and a control unit, wherein the control unit controls the substrate processing apparatus, (a) A control for providing a substrate having a base film and a metal-containing resist film formed on the base film to a substrate support portion of a chamber, wherein the metal-containing resist film has an exposed first region and an unexposed second region, (b) The system is configured to perform control to supply a processing gas to the chamber to develop the substrate and selectively remove the second region from the metal-containing resist film, The control described in (b) above is: (b1) Control to control the temperature of the substrate or the substrate support to a first temperature and perform development, (b2) Control to perform development by controlling the temperature of the substrate or the substrate support to a second temperature different from the first temperature, PCB processing system.

[0171] (Note 26) A substrate processing system comprising a substrate processing apparatus having a chamber and a control unit, wherein the control unit controls the substrate processing apparatus, (a) A control for providing a substrate having a base film and a metal-containing resist film formed on the base film to a substrate support in a chamber, wherein the metal-containing resist film has an exposed first region and an unexposed second region, (b) The system is configured to perform control to supply a processing gas to the chamber to develop the substrate and to selectively remove either the first region or the second region from the metal-containing resist film, The control described in (b) above is: (b1) Control for developing the substrate under the first development conditions, (b2) Control for developing the substrate under second developing conditions different from the first developing conditions, wherein the second developing conditions include control in which at least one of the developing parameters, including the temperature of the substrate, the pressure in the chamber, the flow rate of the processing gas, the type of the processing gas, and the residence time of the processing gas on the substrate, is different from that of the first developing conditions. PCB processing system.

[0172] (Note 27) A device manufacturing method, (a) A step of providing a substrate having a base film and a metal-containing resist film formed on the base film onto a substrate support portion in a chamber, wherein the metal-containing resist film has an exposed first region and an unexposed second region, (b) A step of supplying a processing gas to the chamber to develop the substrate and selectively removing the second region from the metal-containing resist film, The above step (b) is: (b1) A step of developing by controlling the temperature of the substrate or the substrate support to a first temperature, (b) A step of developing by controlling the temperature of the substrate or the substrate support to a second temperature different from the first temperature, Device manufacturing method.

[0173] (Note 28) A device manufacturing method, (a) A step of providing a substrate having a base film and a metal-containing resist film formed on the base film to a substrate support in a chamber, wherein the metal-containing resist film has an exposed first region and an unexposed second region, (b) A step of 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 above step (b) is: (b1) A step of developing the substrate under first developing conditions, (b2) A step of developing the substrate under second developing conditions different from the first developing conditions, wherein at least one of the developing parameters, including the temperature of the substrate or the substrate support, the pressure in the chamber, the flow rate of the processing gas, the type of the processing gas, and the residence time of the processing gas on the substrate, is different from that of the first developing conditions. Device manufacturing method.

[0174] (Note 29) A computer in a substrate processing system having one or more substrate processing devices and a control unit, (a) A control for providing a substrate having a base film and a metal-containing resist film formed on the base film to a substrate support portion of a chamber, wherein the metal-containing resist film has an exposed first region and an unexposed second region, (b) A program that causes the chamber to be supplied with a processing gas to develop the substrate and to selectively remove the second region from the metal-containing resist film, The control described in (b) above is: (b1) Control to control the temperature of the substrate or the substrate support to a first temperature and perform development, (b2) Control to perform development by controlling the temperature of the substrate or the substrate support to a second temperature different from the first temperature, program.

[0175] (Note 30) A computer in a substrate processing system having one or more substrate processing devices and a control unit, (a) A control for providing a substrate having a base film and a metal-containing resist film formed on the base film to a substrate support in a chamber, wherein the metal-containing resist film has an exposed first region and an unexposed second region, (b) A program that causes the chamber to be supplied with a processing gas to develop the substrate and to perform control to selectively remove either the first region or the second region from the metal-containing resist film, The control described in (b) above is: (b1) Control for developing the substrate under the first development conditions, (b2) Control for developing the substrate under second developing conditions different from the first developing conditions, wherein the second developing conditions include control in which at least one of the developing parameters, including the temperature of the substrate or the substrate support, the pressure in the chamber, the flow rate of the processing gas, the type of processing gas, and the residence time of the processing gas on the substrate, is different from that of the first developing conditions. program.

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

[0177] The embodiments described above are for illustrative purposes only and are not intended to limit the scope of this disclosure. Each embodiment can be modified in various ways without departing from the scope and spirit of this disclosure. For example, some components of one embodiment can be added to other embodiments, or some components of one embodiment can be replaced with corresponding components of 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...Aperture, RM...Resist film, RM1...First region, RM2...Second region, UF...Undercoat, W...Substrate

Claims

1. A substrate processing method, (a) A step of providing a substrate having a base film and a metal-containing resist film formed on the base film onto a substrate support portion in a chamber, wherein the metal-containing resist film has an exposed first region and an unexposed second region, (b) A step of supplying a processing gas to the chamber to develop the substrate and selectively removing the second region from the metal-containing resist film, The above step (b) is: (b1) A step of developing by controlling the temperature of the substrate or the substrate support to a first temperature and exposing the substrate to the processing gas, (b2) After step (b1), the process includes developing the substrate by controlling the temperature of the substrate or the substrate support to a second temperature higher than the first temperature and exposing the substrate to the processing gas. Substrate processing method.

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

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

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

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

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

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

8. The substrate processing method according to claim 1, wherein step (b) includes a step of performing a cycle including step (b1) and step (b2) once or more times without generating plasma from the processing gas, and then performing a cycle including step (b1) and step (b2) once or more times with plasma generated from the processing gas.

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

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

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

13. The halogen-containing gases mentioned above are HBr gas and BCl. ３ The substrate processing method according to claim 12, comprising at least one selected from the group consisting of gas, HCl gas, HI gas, and HF gas.

14. The substrate treatment method according to claim 1, wherein the treatment gas comprises a gas containing at least one selected from the group consisting of carboxylic acids, β-dicarbonyl compounds, and alcohols.

15. The gas containing the carboxylic acid 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 O), and the substrate processing method according to claim 14, 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 The substrate processing method according to claim 14, comprising at least one selected from the group consisting of ).

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

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

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

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

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

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

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

24. The substrate processing method according to claim 1, wherein 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 the side wall of the chamber housing the substrate support, the output of a heater in the ceiling of the chamber, the temperature of the heat transfer fluid flowing in the substrate support, the pressure of the heat transfer gas supplied between the back surface of the substrate and the surface of the substrate support, and the output of electromagnetic waves configured to irradiate the 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 processing gas into the chamber, A substrate support section that supports the substrate, The system includes a temperature adjustment unit for adjusting the temperature of the substrate or the substrate support, The control unit, (a) A control for providing a substrate having a base film and a metal-containing resist film formed on the base film to the substrate support portion of the chamber, wherein the metal-containing resist film has an exposed first region and an unexposed second region, (b) The gas supply unit is configured to supply a processing gas to the chamber to develop the substrate and to perform control to selectively remove the second region from the metal-containing resist film, The control described in (b) above is: (b1) Control to control the temperature of the substrate or the substrate support to a first temperature using the temperature adjustment unit, and to develop the substrate by exposing it to the processing gas, (b2) After the control described in (b1), the temperature control unit controls the temperature of the substrate or the substrate support to a second temperature higher than the first temperature, and the substrate is exposed to the processing gas to perform development, including the control described above. PCB processing system.

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