Substrate processing method and substrate processing system

Abstract

Techniques for suppressing residue in a developed pattern are provided. A substrate processing method is provided. The method includes: (a) a step of providing a substrate having a base film and a metal-containing resist film formed on the base film on a substrate support portion in a chamber, the metal-containing resist film having a first region that is exposed and a second region that is not exposed; and (b) a step of supplying a processing gas to the chamber, developing the substrate, and selectively removing the second region from the metal-containing resist film. The step (b) includes: (b1) a step of developing by controlling the temperature of the substrate or the substrate support part at a first temperature; and (b2) a step of developing by controlling the temperature of the substrate or the substrate support part to a second temperature different from the first temperature.

Description

Technical Field

[0001] 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 patternable thin film on a semiconductor substrate using extreme ultraviolet light (hereinafter referred to as “EUV light”).

[0003] Prior art literature

[0004] Patent Literature

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

[0006] The present disclosure provides a technique for suppressing residue in a developed pattern.

[0007] In an exemplary embodiment of the present disclosure, 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 on a substrate support portion in a chamber, wherein the metal-containing resist film has an exposed first area and an unexposed second area; and (b) supplying a processing gas to the chamber, developing the substrate, and selectively removing the second area from the metal-containing resist film, wherein the process (b) comprises: (b1) controlling the temperature of the substrate support portion at a first temperature and performing development; and (b2) controlling the temperature of the substrate support portion at a second temperature different from the first temperature and performing development.

[0008] Effects of the Invention

[0009] According to an exemplary embodiment of the present disclosure, it is possible to provide a technique for suppressing residue in a development pattern. BRIEF DESCRIPTION OF THE DRAWINGS

[0010] Figure 1A It is a diagram for explaining a configuration example of a heat treatment system.

[0011] Figure 1B It is a plan view showing another structural example of the substrate supporting portion.

[0012] Figure 2 This is a diagram for explaining a configuration example in which a plasma processing system is used as a developing processing system.

[0013] Figure 3 It is a diagram for explaining a configuration example of a capacitively coupled plasma processing apparatus.

[0014] Figure 4 is a flowchart showing the present processing method.

[0015] Figure 5 1 is a diagram showing an example of a cross-sectional structure of a substrate W provided in step ST11 .

[0016] Figure 6 FIG. 1 is a diagram showing an example of the base film UF of the substrate W. FIG.

[0017] Figure 7 FIG. 1 is a diagram showing an example of an underfilm UF of a substrate W. FIG.

[0018] Figure 8 1 is a diagram showing an example of a cross-sectional structure of the substrate W after being processed in step ST12.

[0019] Fig. 9 This is a diagram for explaining an example of step ST12.

[0020] Fig.10 It is schematically shown in Fig. 9 A diagram showing an example of a phenomenon occurring on the surface of a substrate W in the example shown.

[0021] Fig.11 This is a diagram for explaining an example of step ST12.

[0022] Fig.12 This is a diagram for explaining an example of step ST12.

[0023] Fig.13 This is a flowchart related to a modified example of the present processing method.

[0024] Fig.14 This is a diagram for explaining an example of step ST12 in the modification example.

[0025] Fig.15 This is a diagram for explaining an example of step ST12 in the modification example.

[0026] Fig.16 It is a graph showing the development results according to Example 1 and Reference Example 1.

[0027] Fig.17 It is a block diagram for explaining a configuration example of a substrate processing system SS.

[0028] Fig.18 is a flow chart illustrating method MT.

[0029] Description of Reference Numerals

[0030] 1…plasma processing device; 2…control unit; 10…plasma processing chamber; 11…substrate support unit; 20…gas supply unit; 30…power supply; 100…heat treatment device; 102…processing chamber; 120…stage heater; 121…substrate support unit; 141…gas nozzle; 200…control unit; OP…opening; RM…resist film; RM1…first region; RM2…second region; UF…base film; W…substrate. DETAILED DESCRIPTION

[0031] Hereinafter, each embodiment of the present disclosure will be described.

[0032] In an 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 on a substrate support portion 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, developing the substrate, and selectively removing the second region from the metal-containing resist film, wherein the process (b) comprises: (b1) controlling the temperature of the substrate or the substrate support portion at a first temperature for development; and (b2) controlling the temperature of the substrate or the substrate support portion at a second temperature different from the first temperature for development.

[0033] In an exemplary embodiment, the second temperature is higher than the first temperature.

[0034] In one exemplary embodiment, in the process (b2), the process gas is not supplied to the chamber, or the flow rate of the process gas supplied to the chamber is smaller than the flow rate of the process gas supplied to the chamber in the process (b1).

[0035] In an exemplary embodiment, the pressure in the chamber in the step (b2) is lower than the pressure in the chamber in the step (b1).

[0036] In an exemplary embodiment, the step (b) further includes a step of purging the processing gas in the chamber between the steps (b1) and (b2).

[0037] In one exemplary embodiment, in the step (b1) and the step (b2), the processing gas is supplied to the chamber at a constant flow rate.

[0038] In an 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 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, developing the substrate, and selectively removing any one of the first region and the second region from the metal-containing resist film, wherein the process (b) comprises: (b1) developing the substrate under a first developing condition and (b2) developing the substrate under a second developing condition different from the first developing condition, at least one of the developing parameters of the second developing condition being different from the first developing condition, 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 relative to the substrate.

[0039] In an exemplary embodiment, in step (b), development is performed using plasma generated from the processing gas, and the development parameters further include a power level of a source RF signal supplied to the chamber for generating plasma and a power or voltage level of a bias signal supplied to the chamber.

[0040] In an exemplary embodiment, the bias signal includes a bias RF signal or a voltage pulse, and the development parameter further includes at least one of a frequency of the source RF signal, a frequency of the bias RF signal, and a frequency of the voltage pulse.

[0041] In an exemplary embodiment, at least one of the source RF signal and the bias RF signal is pulsed, and the development parameters further include at least one of a duty cycle of the pulsed source RF signal and a duty cycle of the pulsed bias signal.

[0042] In one exemplary embodiment, in the process of (b2), two or more development parameters of the second development condition are different from those of the first development condition.

[0043] In one exemplary embodiment, the process of (b1) and the process of (b2) are repeated in the process of (b).

[0044] In one exemplary embodiment, after performing a cycle including the step (b1) and the step (b2) one or more times in the step (b), the step (b1) is further performed.

[0045] In an exemplary embodiment, the process (b) includes generating plasma from the processing gas and performing one or more cycles of the process (b1) and the process (b2) without generating plasma from the processing gas, followed by generating plasma from the processing gas and performing one or more cycles of the process (b1) and the process (b2).

[0046] In an exemplary embodiment, the process (b) includes generating plasma from a processing gas and performing one or more cycles of the process (b1) and the process (b2), and then performing one or more cycles of the process (b1) and the process (b2) without generating plasma from the processing gas.

[0047] In at least one of the step (b1) and the step (b2), the first region or the second region is selectively removed using plasma generated from the processing gas.

[0048] In one exemplary embodiment, the metal-containing resist film includes at least one metal selected from the group consisting of Sn, Hf, and Ti.

[0049] In one exemplary embodiment, the process gas includes a halogen-containing gas.

[0050] In one exemplary embodiment, the acidity of the process gas used in the process (b1) is different from the acidity of the process gas used in the process (b2).

[0051] In one exemplary embodiment, the process of (c) is performed in a chamber different from the chamber used in the process of (b).

[0052] In one exemplary embodiment, the process of (c) is performed in the chamber used in the process of (b).

[0053] In one exemplary embodiment, the first region is EUV exposed.

[0054] The temperature of the substrate or the substrate support portion is controlled by at least one selected from the group consisting of the output of a heater within the substrate support portion, the output of a heater within a side wall of a chamber that accommodates the substrate support portion, the output of a heater within a top of the chamber, the temperature of a heat transfer fluid flowing within the substrate support portion, the pressure of a heat transfer gas supplied between the back side of the substrate and the surface of the substrate support portion, and the output of an electromagnetic wave configured to irradiate the surface of the substrate.

[0055] In an exemplary embodiment, a substrate processing system is provided, comprising a substrate processing device and a control unit, wherein the substrate processing device has a chamber, and the control unit is configured to perform the following control on the substrate processing device: (a) control of providing a substrate having a base film and a metal-containing resist film formed on the base film on a substrate support portion of the chamber, wherein the metal-containing resist film has an exposed first area and an unexposed second area; and (b) control of supplying a processing gas to the chamber, developing the substrate, and selectively removing the second area from the metal-containing resist film, wherein the control of (b) includes: (b1) control of controlling the temperature of the substrate or the substrate support portion to be at a first temperature for development; and (b2) control of controlling the temperature of the substrate or the substrate support portion to be at a second temperature different from the first temperature for development.

[0056] Hereinafter, various embodiments of the present disclosure will be described in detail with reference to the accompanying drawings. In addition, the same symbols are marked on the same or identical elements in each of the drawings, and repeated descriptions are omitted. Unless otherwise specified, the positional relationship of up, down, left, right, etc. is described based on the positional relationship shown in the drawings. The dimensional ratios of the drawings do not represent the actual ratios, and the actual ratios are not limited to the ratios shown in the drawings.

[0057] <Configuration Example of Heat Treatment System>

[0058] Figure 1A 1 is a diagram for explaining a configuration example of a heat treatment system. In one embodiment, the heat treatment system includes a heat treatment apparatus 100 and a controller 200. The heat treatment system is an example of a substrate treatment system, and the heat treatment apparatus 100 is an example of a substrate treatment apparatus.

[0059] The heat treatment apparatus 100 has a processing chamber 102 configured to form a closed space. The processing chamber 102 is, for example, an airtight cylindrical container configured to adjust the internal atmosphere. A side wall heater 104 is provided on the side wall of the processing chamber 102. A top heater 130 is provided on the top wall (top plate) of the processing chamber 102. The top surface 140 of the top wall (top plate) of the processing chamber 102 is formed as a horizontal flat surface, and its temperature is adjusted by the top heater 130.

[0060] A substrate support portion 121 is provided on the lower side of the processing chamber 102. The substrate support portion 121 has a substrate supporting surface thereon for supporting the substrate W. The substrate support portion 121 is formed in a circular shape, for example, when viewed from above, and the substrate W is placed on its surface (upper surface) formed horizontally. A stage heater 120 is embedded in the substrate support portion 121. The stage heater 120 can heat the substrate W placed on the substrate support portion 121. In addition, a ring assembly (not shown) can also be arranged on the substrate support portion 121 in a manner of surrounding the substrate W. The ring assembly can include one or more annular components. By arranging the ring assembly around the substrate W, the temperature controllability of the peripheral area of ​​the substrate W can be improved. Depending on the intended heat treatment, the ring assembly can be composed of an inorganic material or an organic material.

[0061] Figure 1B is a top view showing another structural example of the substrate support portion. In one embodiment, the substrate support portion may be used Figure 1B The substrate support portion 121a shown replaces Figure 1A The substrate support portion 121 is shown. Figure 1B The substrate support portion 121a shown has a plurality of partitions, each of which has a heater electrode. Figure 1B In the example shown, the substrate support portion 121a has zones Z1 to Z14, and a heater electrode is provided in each zone. The heater electrodes of each zone are configured to be able to supply power independently. That is, the substrate support portion 121a is configured to be able to independently control the temperature of each zone. Therefore, according to the substrate support portion 121a, the in-plane uniformity of the resist film RM described later during development can be improved. In addition, according to the substrate support portion 121a, the substrate W can be heated sequentially from the center side to the edge side, or from the edge side to the center side. Furthermore, according to the substrate support portion 121a, a specific area of ​​the substrate W can also be heated to a temperature higher than that of other areas.

[0062] The substrate support part 121 is supported in the processing chamber 102 by a support 122 provided on the bottom surface of the processing chamber 102. A plurality of lifting pins 123 capable of vertical lifting and lowering are provided on the circumferential outer side of the support 122. The plurality of lifting pins 123 are respectively inserted into through holes provided in the substrate support part 121. The plurality of lifting pins 123 are arranged spaced apart in the circumferential direction. The lifting and lowering movement of the plurality of lifting pins 123 is controlled by a lifting mechanism 124. When the lifting pins 123 protrude toward the surface of the substrate support part 121, the substrate W can be transferred between the conveying mechanism (not shown) and the substrate support part 121.

[0063] An exhaust port 131 having an opening is provided on the side wall of the processing chamber 102. The exhaust port 131 is connected to an exhaust mechanism 132 via an exhaust pipe. The exhaust mechanism 132 is composed of a vacuum pump and a valve, etc., and adjusts the exhaust flow rate from the exhaust port 131. The pressure in the processing chamber 102 is adjusted by adjusting the exhaust flow rate and the like through the exhaust mechanism 132. In addition, a transfer port for a substrate W (not shown) is freely formed on the side wall of the processing chamber 102 at a position different from the position where the exhaust port 131 opens.

[0064] In addition, a gas nozzle 141 is provided on the side wall of the processing chamber 102 at a position different from the exhaust port 131 and the transfer port of the substrate W. The gas nozzle 141 supplies the processing gas into the processing chamber 102. The gas nozzle 141 is provided on the side wall of the processing chamber 102 and on the opposite side of the exhaust port 131 when viewed from the center of the substrate support portion 121. That is, the gas nozzle 141 is provided on the side wall of the processing chamber 102 symmetrically with respect to the exhaust port 131 with respect to the vertical virtual plane passing through the center of the substrate support portion 121.

[0065] The gas nozzle 141 is formed in a rod shape protruding from the side wall of the processing chamber 102 toward the center of the processing chamber 102. The front end of the gas nozzle 141 extends horizontally from the side wall of the processing chamber 102. The processing gas is ejected into the processing chamber 102 from the ejection port opened at the front end of the gas nozzle 141, and the gas is ejected along the gas nozzle 141. Figure 1A The gas flows in the direction of the arrow of the dotted line shown in FIG. 1 and is exhausted from the exhaust port 131. In addition, the exhaust port 131 may also be provided at the bottom surface of the processing chamber 102. In addition, the front end portion of the gas nozzle 141 may have a shape extending obliquely downward toward the substrate W, or may have a shape extending obliquely upward toward the top surface 140 of the processing chamber 102.

[0066] The gas nozzle 141 may be disposed on the top wall of the processing chamber 102. A plurality of gas nozzles 141 may be disposed on the top wall. Figure 3 The gas nozzle may be replaced by a nozzle having the same structure as the nozzle 13. The flow rate or type of gas supplied to the substrate W from the plurality of gas nozzles or nozzles may be configured to control each region of the substrate W (e.g. Figure 1B In one embodiment, the flow rate of the gas supplied to the central area of ​​the substrate W may be greater than the flow rate of the gas supplied to the outer area of ​​the substrate W.

[0067] The heat treatment apparatus 100 has a gas supply pipe 152 connected to the gas nozzle 141 from the outside of the processing chamber 102. A pipe heater 160 for heating the gas in the gas supply pipe is provided around the gas supply pipe 152. The gas supply pipe 152 is connected to a gas supply unit 170. The gas supply unit 170 includes at least one gas source and at least one flow controller. The gas supply unit may include a vaporizer that vaporizes a material in a liquid state.

[0068] The control unit 200 processes computer executable instructions that cause the heat treatment device 100 to perform various processes described in the present disclosure. The control unit 200 may be configured to control the various elements of the heat treatment device 100 to perform various processes described herein. In one embodiment, a part or all of the control unit 200 may be included in the heat treatment device 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. The program may be pre-stored in the storage unit 200a2, or may be acquired via a medium when necessary. The acquired program is stored in the storage unit 200a2, and is read and executed from the storage unit 200a2 by the processing unit 200a1. The medium may be various storage media readable by the computer 200a, and may be a communication circuit connected to the communication interface 200a3. The processing unit 200a1 may also be a CPU (Central Processing Unit). The storage unit 200a2 may include a RAM (Random Access Memory), a ROM (Read Only Memory), a HDD (Hard Disk Drive), an SSD (Solid State Drive) or a combination thereof. The communication interface 200a3 may also communicate with the heat treatment device 100 via a communication circuit such as a LAN (Local Area Network).

[0069] <Configuration Example of Plasma Processing System>

[0070] Figure 21 is a diagram for illustrating an example of a configuration when a plasma processing system is used as a development processing system. In one embodiment, the plasma processing system includes a plasma processing device 1 and a controller 2. The plasma processing system is an example of a substrate processing system, and the plasma processing device 1 is an example of a substrate processing device. The plasma processing device 1 includes a plasma processing chamber (hereinafter referred to as a "processing chamber") 10, a substrate support portion 11, and a plasma generating portion 12. The plasma processing chamber 10 has a plasma processing space. In addition, the plasma processing chamber 10 has at least one gas supply port for supplying at least one processing gas to the plasma processing space and at least one gas exhaust port for exhausting gas from the plasma processing space. The gas supply port is connected to the gas supply portion 20 described later, and the gas exhaust port is connected to the exhaust system 40 described later. The substrate support portion 11 is arranged in the plasma processing space and has a substrate supporting surface for supporting a substrate.

[0071] The plasma generating unit 12 is configured to generate plasma by 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: Capacitive Iycoupled Plasma), an inductively coupled plasma (ICP: Inductive Iycoupled Plasma), an ECR plasma (Electron-Cyclotron-Resonance Plasma), a helicon wave excited plasma (HWP: Helicon Wave Plasma) or a surface wave plasma (SWP: Surface Wave Plasma), etc. In addition, various types of plasma generating units including an alternating current (AC) plasma generating unit and a direct current (DC) plasma generating unit may also be used. In one embodiment, the AC signal (AC power) used in the AC plasma generating unit has a frequency in the range of 100kHz to 10GHz. Therefore, the AC signal includes a radio frequency (RF) signal and a microwave signal. In one embodiment, the RF signal has a frequency in the range of 100kHz to 150MHz.

[0072] The control unit 2 processes computer-executable instructions that cause the plasma processing apparatus 1 to perform the various processes described in the present disclosure. The control unit 2 can be configured to control the various elements of the plasma processing apparatus 1 to perform the various processes described herein. In one embodiment, a portion or all of the control unit 2 can be included in the plasma processing apparatus 1. The control unit 2 is implemented, for example, by a computer 2a. The control unit 2 can also include a processing unit 2a1, a storage unit 2a2, and a communication interface 2a3. The various structures of the control unit 2 can be connected to the control unit 200 (see Figure 1A ) have the same structures.

[0073] Hereinafter, a configuration example of a capacitive coupling type plasma processing apparatus will be described as an example of the plasma processing apparatus 1 . Figure 3 It is a diagram for explaining a configuration example of a capacitively coupled plasma processing apparatus.

[0074] 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. In addition, the substrate processing apparatus 1 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 disposed in the plasma processing chamber 10. The shower head 13 is disposed above the substrate support unit 11. In one embodiment, the shower head 13 constitutes at least a portion of the ceiling of the plasma processing chamber 10. The plasma processing chamber 10 has a plasma processing space 10s defined by the shower head 13, the side wall 10a of the plasma processing chamber 10, and the substrate support unit 11. The plasma processing chamber 10 is grounded. The shower head 13 and the substrate support unit 11 are electrically insulated from the frame of the plasma processing chamber 10.

[0075] The substrate support portion 11 includes a main body 111 and a ring assembly 112. The main body 111 has a central area 111a for supporting a substrate W and an annular area 111b for supporting the ring assembly 112. A wafer is an example of a substrate W. The annular area 111b of the main body 111 surrounds the central area 111a of the main body 111 in a plan view. The substrate W is arranged on the central area 111a of the main body 111, and the ring assembly 112 is arranged on the annular area 111b of the main body 111 in a manner of surrounding the substrate W on the central area 111a of the main body 111. Therefore, the central area 111a is also referred to as a substrate supporting surface for supporting the substrate W, and the annular area 111b is also referred to as a ring supporting surface for supporting the ring assembly 112.

[0076] In one embodiment, the main body 111 includes a base 1110 and an electrostatic chuck 1111. The base 1110 includes a conductive component. The conductive component of the base 1110 can function as a lower electrode. The electrostatic chuck 1111 is arranged on the base 1110. The electrostatic chuck 1111 includes a ceramic component 1111a and an electrostatic electrode 1111b arranged in the ceramic component 1111a. The ceramic component 1111a has a central area 111a. In one embodiment, the ceramic component 1111a also includes an annular area 111b. In addition, other components surrounding the electrostatic chuck 1111, such as an annular electrostatic chuck or an annular insulating component, may also have an annular area 111b. In this case, the ring assembly 112 may be arranged on the annular electrostatic chuck or the annular insulating component, and may be arranged on the electrostatic chuck 1111 and the annular insulating component at the same time. In addition, at least one RF / DC electrode connected to the RF power supply 31 and / or the DC power supply 32 described later may also be arranged in the ceramic component 1111a. In this case, at least one RF / DC electrode functions as a lower electrode. When the bias RF signal and / or DC signal described later is provided to at least one RF / DC electrode, the RF / DC electrode is also referred to as a bias electrode. In addition, the conductive component of the base 1110 and at least one RF / DC electrode may also function as a plurality of lower electrodes. In addition, the electrostatic electrode 1111b may also function as a lower electrode. Therefore, the substrate support portion 11 includes at least one lower electrode.

[0077] The ring assembly 112 includes one or more ring components. In one embodiment, the one or more ring components include one or more edge rings and at least one cover ring. The edge ring is formed of a conductive material or an insulating material, and the cover ring is formed of an insulating material.

[0078] In addition, the substrate support portion 11 may also include a temperature control module, which is configured to adjust at least one of the electrostatic chuck 1111, the ring assembly 112 and the substrate to a target temperature. The temperature 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 in the base 1110, and one or more heaters are disposed in the ceramic component 1111a of the electrostatic chuck 1111. In addition, the substrate support portion 11 may also include a heat transfer gas supply portion, which is configured to supply a heat transfer gas to a gap between the back side of the substrate W and the central area 111a. The substrate support portion 11 may also be connected to Figure 1B The substrate support part 121a shown in the figure also has a plurality of partitions, and each partition has a heater electrode. The heater electrode of each partition can be configured to be independently supplied with power. That is, the substrate support part 11 can be configured to be able to independently control the temperature of each partition.

[0079] 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 introduction ports 13c. The processing gas supplied to the gas supply port 13a is introduced into the plasma processing space 10s from the plurality of gas introduction ports 13c through the gas diffusion chamber 13b. In addition, the showerhead 13 includes at least one upper electrode. In addition, the gas introduction unit may include, in addition to the showerhead 13, one or more side gas injection units (SGI: Side Gas Injector) installed in one or more openings formed on the side wall 10a.

[0080] The gas supply unit 20 may include at least one gas source 21 and at least one flow controller 22. In one embodiment, the gas supply unit 20 is configured to supply at least one process gas to the showerhead 13 from the respective gas sources 21 via the respective flow controllers 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 one or more flow modulation devices for modulating or pulsing the flow of at least one process gas.

[0081] The power supply 30 includes a radio frequency power supply 31, which is coupled to the plasma processing chamber 10 via at least one impedance matching circuit. The radio frequency power supply 31 is configured to provide at least one radio frequency signal (radio frequency power) to at least one lower electrode and / or at least one upper electrode. Thus, plasma is formed by at least one processing gas supplied to the plasma processing space 10s. Therefore, the radio frequency power supply 31 can function as at least a part of the plasma generating unit 12. In addition, by supplying a bias radio frequency signal to at least one lower electrode, a bias potential is generated on the substrate W, and the ion components in the formed plasma can be introduced into the substrate W.

[0082] In one embodiment, the RF power supply 31 includes a first RF generating unit 31a and a second RF generating unit 31b. The first RF generating unit 31a is configured to couple with at least one lower electrode and / or at least one upper electrode via at least one impedance matching circuit to generate a source RF signal (source RF power) for plasma generation. In one embodiment, the source RF signal has a frequency in the range of 10 MHz to 150 MHz. In one embodiment, the first RF generating unit 31a may also be configured to generate a plurality of source RF signals with different frequencies. The generated one or more source RF signals are supplied to at least one lower electrode and / or at least one upper electrode.

[0083] The second RF generating unit 31b is configured to couple with at least one lower electrode via at least one impedance matching circuit to generate a bias RF signal (bias RF power). The frequency of the bias RF signal may be the same as or different from the frequency of the 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 100kHz to 60MHz. In one embodiment, the second RF generating unit 31b may also be configured to generate a plurality of bias RF signals with different frequencies. The generated one or more bias RF signals are supplied to at least one lower electrode. In addition, in various embodiments, at least one of the source RF signal and the bias RF signal may be pulsed.

[0084] In addition, 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 generating unit 32a and a second DC generating unit 32b. In one embodiment, the first DC generating unit 32a is configured to be connected to at least one lower electrode to generate a first DC signal. The generated first DC signal is applied to at least one lower electrode. In one embodiment, the second DC generating unit 32b is configured to be connected to at least one upper electrode to generate a second DC signal. The generated second DC signal is applied to at least one upper electrode.

[0085] In various embodiments, the first and second DC signals may be pulsed. In this case, a voltage pulse sequence is applied to at least one lower electrode and / or at least one upper electrode. The voltage pulse may have a pulse waveform of a rectangle, a trapezoid, a triangle, or a combination thereof. In one embodiment, a waveform generating unit for generating a voltage pulse sequence from a DC signal is connected between the first DC generating unit 32a and at least one lower electrode. Therefore, the first DC generating unit 32a and the waveform generating unit constitute a voltage pulse generating unit. In the case where the second DC generating unit 32b and the waveform generating unit constitute a voltage pulse generating unit, the voltage pulse generating unit is connected to at least one upper electrode. The voltage pulse may have a positive polarity or a negative polarity. In addition, the sequence of voltage pulses may include one or more positive polarity voltage pulses and one or more negative polarity voltage pulses in one cycle. In addition, the first and second DC generating units 32a, 32b may be provided on the basis of the RF power supply 31, and the first DC generating unit 32a may also be provided instead of the second RF generating unit 31b.

[0086] The exhaust system 40 may be connected to a gas outlet 10e disposed at the bottom of the plasma processing chamber 10, for example. The exhaust system 40 may include a pressure regulating valve and a vacuum pump. The pressure in the plasma processing space 10s is regulated by the pressure regulating valve. The vacuum pump may include a turbomolecular pump, a dry pump, or a combination thereof.

[0087] <An Example of Substrate Processing Method>

[0088] Figure 4 1 is a flow chart showing a substrate processing method according to an exemplary first embodiment (hereinafter also referred to as “the present processing method”). Figure 4 As shown, the processing method includes a step ST11 of providing a substrate and a step ST12 of developing the substrate. The processing method can be performed in a heat treatment system (refer to Figure 1A ) or a plasma processing system. Next, the control unit 200 controls each part of the heat treatment apparatus 100 to perform the processing method on the substrate W as an example for description.

[0089] (Step ST11: Providing a Substrate)

[0090] First, in step ST11, a substrate W is provided in the processing chamber 102 of the heat treatment apparatus 100. The substrate W is provided on the substrate support 121 via the lifting pins 123. After the substrate W is arranged 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 can be performed by controlling the output of one or more heaters among the side wall heater 104, the stage heater 120, the top heater 130 and the pipe heater 160 (hereinafter collectively referred to as "each heater"). In one example, the temperature of the substrate support 121 can be adjusted to the set temperature before step ST11. That is, the substrate W can be provided on the substrate support 121 after the temperature of the substrate support 121 is adjusted to the set temperature.

[0091] Figure 5 1 is a diagram showing an example of a cross-sectional structure of a substrate W provided in step ST11. The substrate W includes an underfilm UF and a resist film RM formed on the underfilm UF. The substrate W can be used to manufacture semiconductor devices. The semiconductor devices include memory devices such as DRAM and 3D-NAND flash memory and logic devices.

[0092] like Figure 5 As shown, the resist film RM has an exposed first region RM1 and an unexposed second region RM2. The first region RM1 is an EUV exposure region where EUV exposure is performed by EUV. The second region RM2 is an unexposed region that is not EUV exposed. The film thickness of the first region RM1 may be less than the film thickness of the second region RM2.

[0093] The resist film RM is a metal-containing resist film containing a metal. In one example, the metal may include at least one metal selected from the group consisting of Sn, Hf, and Ti. In one example, the resist film RM may contain Sn, including tin oxide (SnO) and tin hydroxide (Sn-OH bond). The resist film RM may also contain an organic substance.

[0094] The base film UF may be an organic film, a dielectric film, a metal film, a semiconductor film or a stacked film thereof formed on a silicon wafer. In one embodiment, the base film UF includes at least one selected from the group consisting of a silicon-containing film, a carbon-containing film and a metal-containing film.

[0095] Figure 6 and Figure 7 1 and 2 are diagrams showing an example of a bottom film UF of a substrate W. Figure 6 As shown, the bottom membrane UF can be composed of a first membrane UF1, a second membrane UF2 and a third membrane UF3. Figure 7 As shown, the bottom membrane UF can be composed of a second membrane UF2 and a third membrane UF3.

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

[0097] In one embodiment, the substrate W is formed as follows. First, a photoresist film containing a metal is formed on a base film to which adhesion treatment has been applied, etc. The film formation can be performed by a dry method, by a wet method such as solution coating, or by both a dry method and a wet method. In addition, before the photoresist film is formed, a surface modification treatment of the base film may be included. The substrate after the photoresist film is formed is subjected to a heating treatment, i.e., a pre-baking (Post Applied Bake: PAB). Additional heating treatment may also be applied to the pre-baked substrate. The substrate after the heating treatment is transported to an exposure device, and the photoresist film is irradiated with EUV light via an exposure mask (photomask). Thus, a substrate W is formed, which has a base 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 on the exposure mask (photomask). The second region RM2 is a region corresponding to a pattern provided on the exposure mask (photomask). EUV has a wavelength in the range of 10 to 20 nm, for example. EUV can have a wavelength in the range of 11 to 14 nm, and in one example has a wavelength of 13.5 nm. The exposed substrate is transported from the exposure device to a heat treatment device under environmental gas management and subjected to a heat treatment, i.e., post-exposure baking (PEB). Additional heat treatment can also be performed on the substrate W after PEB.

[0098] (Step ST12: Development of Substrate)

[0099] Next, in step ST12, the resist film RM of the substrate W is developed. In the present processing method, the second region RM2 can be selectively removed by development. In one embodiment, step ST12 includes step ST120 of developing the substrate at a first temperature, step ST121 of developing the substrate at a second temperature different from the first temperature, and step ST122 of determining whether a stop condition is satisfied.

[0100] (Step ST120: Developing the Substrate at the First Temperature)

[0101] First, in step ST120, a processing gas is supplied into the processing chamber 102 via a gas nozzle 141. In one embodiment, the processing gas includes a halogen-containing gas. The halogen-containing gas may be a gas containing a halogen-containing inorganic acid, or may be an inorganic acid gas containing Br or Cl. The gas containing a halogen-containing inorganic acid may be a gas containing a hydrogen halide and / or a boron halide. In one example, the gas containing a halogen-containing inorganic acid 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 processing gas may be a gas containing an organic acid. The gas containing an organic acid may, for example, be a gas containing at least one selected from the group consisting of a carboxylic acid, a β-dicarbonyl compound, and an alcohol. In one embodiment, the processing gas is a gas containing a carboxylic acid. In one example, the carboxylic acid may be formic acid (HCOOH), acetic acid (CH3COOH), trichloroacetic acid (CCl3COOH), monofluoroacetic acid (CFH2COOH), difluoroacetic acid (CF2FCOOH), trifluoroacetic acid (CF3COOH) monochlorodifluoroacetic acid (CClF2COOH), sulfur-containing acetic acid, thioacetic acid (CH3COSH), mercaptoacetic acid (HSCH2COOH), trifluoroacetic anhydride ((CF3CO)2O) and acetic anhydride ((CH3CO)2O). In one embodiment, the process gas comprises a β-dicarbonyl compound. In one example, the β-dicarbonyl compound can be acetylacetone (CH3C(O)CH2C(O)CH3), trichloroacetylacetone (CCl3C(O)CH2C(O)CH3), hexachloroacetylacetone (CCl3C(O)CH2C(O)CCl3), trifluoroacetylacetone (CF3C(O)CH2C(O)CH3) and hexafluoroacetylacetone (HFAc, CF3C(O)CH2C(CF3). In one embodiment, the first processing gas contains an alcohol. The alcohol can be perfluorotert-butyl alcohol ((CF3)3COH) in one example.

[0102] In one embodiment, the treatment gas is a gas containing trifluoroacetic acid. In one embodiment, the treatment gas contains halogenated organic acid vapor. The treatment gas in one example contains at least one selected from the group consisting of trifluoroacetic anhydride, acetic anhydride, trichloroacetic acid, CFH2COOH, CF2HCOOH, monochlorodifluoroacetic acid, sulfur-containing acetic acid, thioacetic acid and mercaptoacetic acid. In one embodiment, the treatment gas is a mixed gas of carboxylic acid and hydrogen halide or a mixed gas of acetic acid and formic acid. In one embodiment, the treatment gas is a gas containing acetic acid.

[0103] In step ST120, the temperature of the substrate W or the substrate support 121 is controlled at a first temperature. The temperature adjustment of the substrate W or the substrate support 121 can be performed by controlling the output of one or more of the heaters. The first temperature can be appropriately selected within the range of removing the second region RM2 with a sufficient selectivity relative to the first region RM1. The first temperature can be appropriately selected according to the type of processing gas. For example, when HBr gas is used as the processing gas, the first temperature can be, for example, above 10°C and below 30°C, above 10°C and below 20°C, and in one example, 10°C. Step ST120 can be performed until a given period has passed, or until the second region RM is removed to a given depth. The given period can be, for example, above 0.1 seconds and below 300 seconds, above 0.1 seconds and below 60 seconds, or above 60 seconds and below 300 seconds.

[0104] (Step ST121: Developing the Substrate at the Second Temperature)

[0105] In step ST121, the temperature of the substrate W or the substrate support 121 is controlled at a second temperature different from the first temperature. The temperature adjustment of the substrate W or the substrate support 11 can be performed by controlling the output of one or more of the heaters. In one embodiment, the second temperature may be a temperature higher than the first temperature. The second temperature may be appropriately selected according to the type of process gas. For example, when HBr gas is used as the process gas, it may be above 40°C and below 100°C, or it may be above 50°C and below 100°C, and in one example, it may be 60°C.

[0106] In step ST121, the process gas may be supplied into the process chamber 102 through the gas nozzle 141. In one embodiment, the flow rate of the process gas is smaller than the flow rate of the process gas in step ST120. In step ST121, the process gas may not be supplied into the process chamber 102.

[0107] When a processing gas is supplied in step ST121, the type of processing gas may be the same as or different from the processing gas in step ST120. In one embodiment, the acidity of the processing gas supplied in step ST121 is less than that in step ST120. That is, in step ST121, a processing gas having a larger acid dissociation constant (pKa) than the processing gas used in step ST120 may be used. For example, the processing gas may be changed from HBr gas or BCl3 (step ST120) to a carboxylic acid gas such as acetic acid gas (step ST121). In addition, in step ST121, the flow rate (partial pressure) of the processing gas having a larger acid dissociation constant (pKa) may be increased compared to the flow rate (partial pressure) of the processing gas used in step ST120. For example, in the case where the processing gas is a mixed gas of HBr gas and carboxylic acid gas in steps ST120 and 121, the flow rate (partial pressure) of the carboxylic acid gas may be increased in step ST121.

[0108] In step ST121, the pressure in the processing chamber 102 may be the same as or different from that in step ST120. In one embodiment, the pressure in the processing chamber 102 in step ST121 is lower than the pressure in the processing chamber 102 in step ST120. For example, the pressure in the processing chamber 102 in step ST120 may be greater than 50 mTorr and less than 500 mTorr, greater than 50 mTorr and less than 400 mTorr, or greater than 50 mTorr and less than 300 mTorr. For example, the pressure in the processing chamber 10 in step ST121 may be greater than 0.1 mTorr and less than 100 mTorr, or greater than 50 mTorr and less than 100 mTorr.

[0109] Step ST121 may be performed for a given period (for example, from 0.1 seconds to 300 seconds, from 0.1 seconds to 60 seconds, or from 60 seconds to 300 seconds) or until the second region RM of a given depth is removed.

[0110] (Step ST122: Judgment)

[0111] In process ST122, it is determined whether a given condition for ending process ST12 is satisfied. In process ST122, if it is determined that the given condition is not satisfied, the process returns to process ST120, and if it is determined that the given condition is satisfied, the process ST12 is ended. The given condition may be, for example, a cycle including process ST120 and process ST121 repeated a preset number of times. The number may be one or more times. The given condition may be, for example, a condition related to the development time, that is, the time elapsed from the start of process ST12. The given condition may be, for example, a condition related to the depth or aspect ratio of the opening or recess formed on the resist film RM after process ST121. At this time, after process ST121, it can be determined whether the size of the resist film RM has reached a given value or range, and the cycle of process ST120 and process ST121 is repeated until the given value or range is reached. The size of the resist film RM can be measured with an optical measuring device.

[0112] In one embodiment, after executing a cycle including step ST120 and step ST121 one or more times, in addition to after step ST121 ends, a determination of whether a given condition is satisfied may be performed after step ST120 ends. Furthermore, if it is determined that the given condition is satisfied, step ST121 may be terminated without executing step ST121.

[0113] In one embodiment, a step of purging the gas in the processing chamber 102 from the exhaust port 131 (hereinafter also referred to as a "purging step") may be performed between steps ST120 and ST121. At this time, an inert gas or the like may be supplied into the processing chamber 102. Thus, the gas of the reaction product generated by the development or the excess processing gas or the like is purged.

[0114] Figure 8 1 is a diagram showing an example of a cross-sectional structure of a substrate W after processing in step ST12. Figure 8 In the example shown, the second region RM2 of the resist film RM is removed to form an opening OP. The opening OP is limited by the side of the first region RM1. The opening OP is a space on the base film UF surrounded by the side. The opening OP has a shape corresponding to the second region RM2 when viewed from above the substrate W (the result is a shape corresponding to the exposure mask pattern for EUV exposure). The shape can be, for example, a circle, an ellipse, a rectangle, a line, or a combination of one or more thereof. A plurality of openings OP can be formed on the resist film RM. A plurality of openings OP may have a linear shape, or may be arranged at certain intervals to form a pattern of lines and intervals. In addition, a plurality of openings OP may be arranged in a lattice to form a column pattern.

[0115] According to the processing method, the temperature of the substrate W or the substrate support 121 is changed in step ST120 and step ST121. Thus, the volatilization amount of the reaction product generated during development can be adjusted. Therefore, it is possible to suppress the reaction product from not volatilizing and thus reducing the development speed or generating residues after development.

[0116] Fig. 9 1 is a diagram for explaining an example of step ST12. Fig. 9 In the figure, the horizontal axis represents time. In addition, the vertical axis represents the flow rate [sccm] of the processing gas supplied to the processing chamber 102, the pressure [Torr] in the processing chamber 102, and the temperature [°C] of the substrate support portion 121. The flow rate "Q1" of the processing gas indicates that the processing gas is not supplied, or is less than the flow rate shown by "Q2". The pressure "P1" in the processing chamber 102 indicates that the pressure is lower than "P2". The temperature "T1" of the substrate support portion 121 indicates a temperature lower than "T2". "T1" corresponds to the first temperature, and "T2" corresponds to the second temperature. Fig. 9 This is an example of a case where the temperature of the substrate support 121 is alternately changed between "T1" (step ST120) and "T2" (step ST121) while maintaining the flow rate of the processing gas and the pressure in the processing chamber 102 constant in step ST12.

[0117] Fig.10 It is schematically shown in Fig. 9 FIG. 1 is a diagram showing an example of a phenomenon occurring on the surface of the substrate W in the example shown. In step ST120, the reaction product R generated by the reaction between the resist film in the second region RM2 and the processing gas is volatilized, and the second region RM2 is removed. As the development progresses, the recess formed on the resist film RM becomes deeper, and sometimes the reaction product R is retained in the recess, and the internal pressure rises, thereby suppressing the volatilization of the reaction product R. In this regard, Fig. 9 In the example shown, in step ST121, the temperature of the substrate support 121 is set to a higher temperature (T2>T1) than in step ST120 to perform development. Fig.10 As shown in FIG. 1 , the volatilization of the reaction product R is promoted compared with step ST120 . This can prevent the reaction product R from being retained in the concave portion and thus reducing the development speed.

[0118] If the development is continued at a high temperature, the development speed of the first region RM1 increases, and the first region RM1 can be removed together with the second region RM2. Fig. 9In the example shown, since the low temperature (T1) development in step ST120 and the high temperature (T2) development in step ST121 are repeated alternately, the development at high temperature (T2) is avoided. Thus, excessive removal of the first region RM1 and reduction of the film thickness can be suppressed. That is, the selectivity of the development (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.

[0119] Fig.11 This is a diagram for explaining an example of step ST12. Fig.11 The vertical and horizontal axes are Fig. 9 same. Fig.11 The example shown is similar to Fig. 9 The example shown is different in that in step ST121 , the processing gas is not supplied or is supplied at a flow rate smaller than that in step ST120 .

[0120] exist Fig.11 In the example shown, Fig. 9 Similarly to the example shown, in step ST121, the temperature of the substrate support 121 is set to a higher temperature (T2>T1) than in step ST120 to perform development. Therefore, compared with step ST120, the volatilization of the reaction product R is promoted. This can prevent the reaction product R from being retained in the concave portion and reducing the development speed. In addition, in Fig.11 In the example shown, Fig. 9 In the example shown, since the low temperature (T1) development in step ST120 and the high temperature (T2) development in step ST121 are repeated alternately, the development at high temperature (T2) is avoided. Fig.11 In the example shown, in the high temperature (T2) development of step ST121, the supply amount of the processing gas is reduced or becomes zero compared to step ST120. As a result, the increase in the development speed of the first region RM1 caused by the increase in the temperature of the substrate support part 121 can be alleviated. By the above, excessive removal of the first region RM1 can be suppressed to reduce the film thickness. That is, the selectivity of the development (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.

[0121] In addition, Fig.11 In the example shown, the timing of the increase (decrease) of the flow rate of the processing gas and the decrease (increase) of the temperature of the substrate support portion are consistent, but the timings may be completely or partially different (the phases may also be offset). That is, in step ST121, the period during which the flow rate of the processing gas is Q1 and the period during which the temperature of the substrate support portion is T2 may overlap at least a part.

[0122] Fig.12 This is a diagram for explaining an example of step ST12. Fig.12The vertical and horizontal axes are Fig. 9 same. Fig.12 The example shown is similar to Fig.11 The illustrated example is different in that a purge step is included between step ST120 and step ST121 , and in step ST121 , the pressure ( P1 ) in the processing chamber 102 is lower than the pressure ( P2 ) in step ST120 .

[0123] exist Fig.12 In the example shown, Fig. 9 In step ST121, the temperature of the substrate support 121 is developed at a higher temperature (T2>T1) than in step ST120. Therefore, the volatilization of the reaction product R is promoted compared with step ST120. Fig.12 In the example shown, a purge step is performed between step ST120 and step ST121. This can prevent the reaction product R from being retained in the concave portion and reducing the development speed. Fig.12 In the example shown, Fig. 9 As in the example shown, since the low temperature (T1) development in step ST120 and the high temperature (T2) development in step ST121 are repeated alternately, the development at high temperature (T2) is avoided. Fig.12 In the example shown, in the development at high temperature (T2) of step ST121, the supply amount of the processing gas is reduced or becomes zero compared to step ST120, and the pressure in the processing chamber 102 is reduced compared to step ST120. As a result, the increase in the development speed of the first region RM1 caused by the increase in the temperature of the substrate support part 121 can be alleviated. By doing so, it is possible to suppress excessive removal of the first region RM1 and reduce the film thickness. In addition, Fig.12 In the example shown, the timing of increasing the flow rate of the processing gas, increasing the pressure in the chamber, and decreasing the temperature of the substrate support unit is consistent, but the timings may be completely or partially different (the phases may also be offset). That is, in step ST121, 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 unit is T2 may overlap.

[0124] In one embodiment, the present treatment method may be performed using a plasma treatment system (see Figure 2 and Figure 3). For example, by providing a substrate W on a substrate support 11 in a processing chamber 10 of a plasma processing device 1 (process ST11), the temperature of the substrate W or the substrate support 11 can be adjusted by a temperature control module to develop the resist film RM (process ST12). In addition, the temperature of the substrate W or the substrate support 11 can also be adjusted by controlling the pressure of a heat transfer gas (such as He) between the electrostatic chuck 1111 and the back side of the substrate W. The processing gas used in process ST12 can be the same as that in the case of using a thermal treatment system. In processes ST120 and / or ST121, development can be performed by generating plasma from the processing gas. That is, a source RF signal can be supplied to the lower electrode of the substrate support 11 and / or the upper electrode of the nozzle 13. At this time, a bias signal can also be supplied to the lower electrode of the substrate support 11.

[0125] In one embodiment, the development treatment in step ST12 may be performed by both heat treatment and plasma treatment. For example, after performing one or more cycles of performing steps ST120 and ST121 by heat treatment (hereinafter also referred to as "heat treatment cycles"), one or more cycles of performing steps ST120 and ST121 by plasma treatment (hereinafter also referred to as "plasma treatment cycles") may be performed. In addition, for example, after performing one or more plasma treatment cycles, one or more heat treatment cycles may be performed. In addition, for example, heat treatment cycles and plasma treatment cycles may be performed alternately multiple times. In addition, for example, step ST120 may be performed by heat treatment and step ST121 may be performed by plasma treatment, or step ST120 may be performed by plasma treatment and step ST121 may be performed by heat treatment.

[0126] In one embodiment, in step ST12, instead of adjusting the temperature of the substrate support (substrate support 121 or substrate support 11), the temperature of the substrate W in step ST121 may be different from the temperature of the substrate W in step ST120 by directly heating the substrate W. For example, a device for generating electromagnetic waves such as infrared light or microwaves may be provided in the heat treatment apparatus 100 or the plasma treatment apparatus 1, and the temperature of the substrate W may be adjusted by irradiating the substrate W with electromagnetic waves through the device.

[0127] In one embodiment, the processing method may include a desorption process. The desorption process includes removing scum from the surface of the resist film RM and the surface of the base film UF or smoothing the surface of the resist film RM by plasma such as an inert gas or an inert gas. The desorption process may be performed after the process ST12. The desorption process may be repeated one or more times between the development and the development in the process ST12. In addition, the desorption process may also be performed, for example, by exposing the substrate W to a plasma generated in the plasma processing device 1. The desorption process may be performed, for example, by introducing a processing gas excited by a remote plasma source into the processing chamber 102 of the thermal processing device 100. In one example, the inert gas is a rare gas such as He, Ar, Ne, Kr, Xe, or nitrogen.

[0128] In one embodiment, the processing method may include a step of etching the base film UF after the step ST12. Etching may be performed, for example, by generating plasma from a processing gas in the processing chamber 10 of the plasma processing device 1. During etching, the resist film RM functions as a mask to form a recess on the base film UF according to the shape of the opening OP. In addition, when developing using the plasma processing device 1 in the step ST12, the etching process may be continuously performed in the same processing chamber 10 as the step ST12, or may be performed in a processing chamber 10 of another plasma processing device 1.

[0129] Fig.13 : is a flowchart related to a modified example of the processing method. Fig.13 As shown, step ST12 may include step ST120A for developing the substrate under the first developing condition and step ST121A for developing the substrate under the second developing condition to replace the above-mentioned steps ST120 and ST121. Figure 1A ) or plasma processing system (refer to Figure 2 , Figure 3 ) is executed.

[0130] The second developing condition is different from the first developing condition in at least one developing parameter. In one embodiment, the second developing condition has more than two different developing parameters. The developing 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. When the volume of the processing chamber is V, the pressure in the processing chamber is P, and the flow rate of the processing gas is Q, the residence time is expressed as (P×V) / Q. When using a plasma processing system (refer to Figure 2 and Figure 3)When the present processing method is performed, the development parameters may further include the power level of the source RF signal supplied to the processing chamber 10 for plasma generation 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. In the case where the source RF signal is pulsed, the development parameters may further include the duty cycle of the pulsed source RF signal. In the case where the bias signal is a bias RF signal, the development parameters may further include the frequency of the bias RF signal. In the case where the bias RF signal is pulsed, the development signal may further include the duty cycle of the pulsed bias RF signal. In the case where the bias signal includes a voltage pulse, the development parameters may further include the frequency (pulse frequency) or duty cycle of the voltage pulse.

[0131] Fig.14 FIG. 1 is a diagram for explaining an example of step ST12 in a modified example. Fig.14 In the figure, the horizontal axis represents time. In addition, the vertical axis represents the flow rate [sccm] of the processing gas supplied to the processing chamber (102, 10) and the pressure [mTorr] in the processing chamber (102, 10). The flow rate "Q1" of the processing gas indicates that the processing gas is not supplied, or the flow rate is smaller than that shown by "Q2". The pressure "P1" in the processing chamber 102 indicates that the pressure is lower than "P2". Fig.14 This is an example of a case where the flow rate of the processing gas and the pressure in the processing chamber are different in the development parameters of the first development condition and the second development condition. In addition, the remaining development parameters may be the same in the development condition 1 and the development condition 2. Fig.14 In the example shown, the timing of the increase (decrease) of the flow rate of the processing gas and the decrease (increase) of the pressure in the chamber are consistent, but the timings may be completely or partially different (the phases may also be offset). That is, in step ST121A, at least a part of the period when the flow rate of the processing gas is Q1 and the period when the pressure in the chamber is P2 may overlap.

[0132] Fig.15 FIG. 1 is a diagram for explaining an example of step ST12 in a modified example. Fig.15 In the figure, the horizontal axis represents time. In addition, the vertical axis represents the flow rates [sccm] of the first gas G1 and the second gas G2 contained in the processing gas supplied to the processing chamber (102, 10). The flow rate "Q1" 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". The flow rate "Q3" 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". Fig.15This is an example of a case where the types of processing gases in the development parameters of the first development condition and the second development condition are different. In one embodiment, the second gas uses 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 lower than the acidity of the processing gas used in step ST120A. In addition, the remaining development parameters can be the same in development condition 1 and development condition 2. In addition, Fig.15 In the example shown, the timing of the increase (decrease) of the flow rate of the first processing gas and the decrease (increase) of the second processing gas are consistent, but the timings may be completely or partially different (the phases may also be offset). That is, in step ST121, at least a part 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 may overlap.

[0133] In the above exemplary embodiment, in the development of step ST12, the second region RM2 of the resist film RM is selectively removed relative to the first region RM1. However, the present processing method is not limited thereto. In one embodiment, in the development of step ST12, the first region RM1 of the resist film RM may be selectively removed relative to the second region RM2.

[0134] <Example>

[0135] Next, examples of the present treatment method are described. The present disclosure is not limited in any way by the following examples.

[0136] (Example 1)

[0137] In Example 1, a plasma processing apparatus 1 (see Figure 3 ) This treatment method (refer to Figure 4 ) is applied to the substrate W (refer to Figure 5 ) and develop the resist film RM.

[0138] In step ST11, a substrate W is provided on the substrate support 11 in the processing chamber 10. The resist film RM of the substrate W is an organic film containing Sn, and has a first region RM1 exposed to EUV and a second region RM2 not exposed to EUV. The base film UF of the substrate W is a silicon oxide film. In addition, the film thickness of the second region RM2 is about 1.3 times greater than the film thickness of the first region RM1.

[0139] The process ST12 includes a process ST120, a purge process, and a process ST122. In the process ST12, a source RF signal and a bias signal are not supplied. That is, in the process ST12, plasma is not generated from the processing gas.

[0140] The step ST120 is performed for 60 seconds. In the step ST120 , the substrate support 11 is adjusted to 10° C. The processing gas includes HBr gas and Ar gas. The pressure in the processing chamber 10 is maintained at 200 mTorr.

[0141] The purge process was performed for 30 seconds using Ar gas. The pressure in the processing chamber 10 was maintained below 10 mTorr.

[0142] The step ST121 is performed for 60 seconds. In the step ST121, the substrate support 11 is adjusted to 60°C. The processing gas includes Ar gas. The pressure in the processing chamber 10 is maintained at 10 mTorr or less.

[0143] (Reference Example 1)

[0144] In Reference Example 1, a plasma processing apparatus 1 (refer to Figure 3 ) to the substrate W (refer to Figure 5 ) is developed. The development is continuously performed under the same conditions as step ST120 of Example 1 (the temperature of the substrate support 11 is 10° C., the pressure of the processing chamber 10 is 200 mTorr, and the processing gas contains HBr gas and Ar gas). That is, in Reference Example 1, unlike Example 1, the purge step and step ST121 are not performed.

[0145] Fig.16 1 is a graph showing the development results of Example 1 and Reference Example 1. Fig.16 In the figure, "t [seconds]" on the horizontal axis represents the development time [seconds], and "D [au]" on the vertical axis represents the standardized film thickness of the resist film RM (ratio to the reference thickness). E1 (RM1) represents the result of the first region RM1 of Example 1, and E1 (RM2) represents the result of the second region RM2 of Example 1. R1 (RM1) represents the result of the first region RM1 of Reference Example 1, and R1 (RM2) represents the result of the second region RM2 of Reference Example 1.

[0146] like Fig.16As shown, in Example 1, the second region RM2 is selectively removed by process ST120 (0 to 60 seconds), a purge process (60 seconds to 90 seconds), process ST121 (90 seconds to 150 seconds), and a second process ST120 (150 seconds to 180 seconds). The reduction in film thickness in the first region RM1 is limited, and a development contrast is also obtained. In contrast, in Reference Example 1, as the development time passes, the development speed of the second region RM2 decreases, and the development contrast with the first region RM1 cannot be obtained, and the second region RM2 cannot be selectively removed. In Example 1, it is believed that by including a purge process and raising the temperature of the substrate support portion 11 in process ST121, the reaction product can be suppressed from being retained in the recess during development, thereby promoting the development of the second region RM2. In addition, in Example 1, in process ST121, the processing gas does not contain HBr gas, and the pressure of the processing chamber 10 is maintained lower than that of process ST120. It is considered that this alleviates the influence of the increase in the development speed due to the increase in the temperature of the substrate supporting portion 11 and suppresses the removal of the first region RM1.

[0147] <Configuration Example of Substrate Processing System>

[0148] Fig.17 This is a block diagram for explaining a configuration example of a substrate processing system SS according to an exemplary embodiment. The substrate processing system SS includes: a first carrier station CS1, a first processing station PS1, a first interface station IS1, an exposure device EX, a second interface station IS2, a second processing station PS2, a second carrier station CS2, and a control unit CT.

[0149] The first carrier station CS1 carries in or carries out the first carrier C1 between the first carrier station CS1 and the external system of the substrate processing system SS. The first carrier station CS1 has a loading table including a plurality of first loading plates ST1. On each first loading plate ST1, a first carrier C1 in a state of accommodating a plurality of substrates W or in an idle state is placed. The first carrier C1 has a frame capable of accommodating a plurality of substrates W therein. In one example, the first carrier C1 is a FOUP (Front Opening Unified Pod).

[0150] In addition, the first carrier station CS1 transfers the substrate W between the first carrier C1 and the first processing station PS1. The first carrier station CS1 also includes a first transfer device HD1. The first transfer device HD1 is arranged between the loading table and the first processing station PS1 in the first carrier station CS1. The first transfer device HD1 transfers and transfers the substrate W between the first carrier C1 on each first loading plate ST1 and the second transfer device HD2 of the first processing station PS1. The substrate processing system SS may also include a load lock module. The load lock module may be arranged between the first carrier station CS1 and the first processing station PS1. The load lock module may switch its internal pressure to atmospheric pressure or vacuum. "Atmospheric pressure" may be the pressure inside the first transfer device HD1. "Vacuum" may be a pressure lower than atmospheric pressure, such as a medium vacuum of 0.1Pa-100Pa. The interior of the second transfer device HD2 may be atmospheric pressure or vacuum. The load lock module can, for example, transfer the substrate W from the first transfer device HD1 under atmospheric pressure to the second transfer device HD2 under vacuum, and can also transfer the substrate W from the second transfer device HD2 under vacuum to the first transfer device HD1 under atmospheric pressure.

[0151] The first processing station PS1 performs various processes on the substrate W. In one embodiment, the first processing station PS1 includes a pre-processing module PM1, a resist film forming module PM2, and a first heat treatment module PM3 (hereinafter collectively referred to as "first substrate processing module PMa"). In addition, the first processing station PS1 has a second conveying device HD2 for conveying the substrate W. The second conveying device HD2 conveys 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.

[0152] In the pre-processing module PM1, the substrate W is pre-processed. In one embodiment, the pre-processing module PM1 includes a temperature adjustment unit for adjusting the temperature of the substrate W, a high-precision temperature adjustment unit for adjusting the temperature of the substrate W with high precision, etc. In one embodiment, the pre-processing module PM1 includes a surface modification unit for performing surface modification on the substrate W. Each treatment unit of the pre-processing module PM1 may include a heat treatment device 100 (see Figure 1A )、Plasma processing device 1 (refer to Figure 2 and 3 ) and / or spin coating and other liquid processing devices.

[0153] In the resist film forming module PM2, a resist film is formed on the substrate W. In one embodiment, the resist film forming module PM2 includes a dry coating unit. The dry coating unit forms the resist film on the substrate W using a dry process such as a vapor deposition method. In one example, the dry coating unit includes a CVD device or an ALD device for chemically evaporating a resist film on the substrate W disposed in the chamber, or a PVD device for physically evaporating a resist film. The dry coating unit may be a thermal processing device 100 (see FIG. 1 ) or a plasma processing device 1 (see FIG. 2 ). Figure 2 and 3 ).

[0154] In one embodiment, the resist film forming module PM2 includes a wet coating unit. The wet coating unit forms a resist film on the substrate W using a wet process such as a liquid deposition method. In one example, the wet coating unit may be a liquid processing device such as a spin coating method.

[0155] In one embodiment, examples of the resist film forming module PM2 include both a wet coating unit and a dry coating unit.

[0156] In the first thermal treatment module PM3, the substrate W is thermally treated. In one embodiment, the first thermal treatment module PM3 includes any one or more of a pre-baking (PAB) unit for heating the substrate W on which the resist film is formed, a temperature adjustment unit for adjusting the temperature of the substrate W, and a high-precision temperature adjustment unit for highly accurately adjusting the temperature of the substrate W. Each of these units may have one or more thermal treatment devices. In one example, a plurality of thermal treatment devices may be stacked. The thermal treatment device may be, for example, the thermal treatment device 100 (see Figure 1A ). Each heat treatment can be performed at a predetermined temperature using a predetermined gas.

[0157] The first interface station IS1 includes a third transport device HD3. The third transport device HD3 transports and delivers the substrate W between the first processing station PS1 and the exposure device EX. The third transport device HD3 may have a frame for accommodating the substrate W, and may be configured to control the temperature, humidity, pressure, etc. in the frame.

[0158] The exposure device EX uses an exposure mask (photomask) to expose the resist film on the substrate W. The exposure device EX may be, for example, an EUV exposure device having a light source that generates EUV light.

[0159] The second interface station IS2 has a fourth transport device HD4. The fourth transport device HD4 transports and delivers the substrate W between the exposure apparatus EX and the second processing station PS2. The fourth transport device HD4 may have a frame for accommodating the substrate W, and may be configured to control the temperature, humidity, pressure, etc. in the frame.

[0160] The second processing station PS2 performs various processes on the substrate W. In one embodiment, the second processing station PS2 includes a second thermal processing module PM4, a measurement module PM5, a development module PM6, and a third thermal processing module PM7 (hereinafter collectively referred to as "second substrate processing module PMb"). In addition, the second processing station PS2 has a fifth conveying device HD5 for conveying the substrate W. The fifth conveying device HD5 conveys and transfers the substrate W between two designated second substrate processing modules PMb and between the second processing station PS2 and the second carrier station CS2 or the second interface station IS2.

[0161] In the second heat treatment module PM4, the substrate W is heat treated. In one embodiment, the heat treatment module PM4 includes any one or more of a post-exposure baking (PEB) unit for heating the exposed substrate W, a temperature adjustment unit for adjusting the temperature of the substrate W, and a high-precision temperature adjustment unit for adjusting the temperature of the substrate W with high precision. Each of these units may have one or more heat treatment devices. In one example, a plurality of heat treatment devices may be stacked. The heat treatment device may be, for example, the heat treatment device 100 (see Figure 1A ). Each heat treatment can be performed at a predetermined temperature using a predetermined gas.

[0162] In the measurement module PM5, various measurements are performed on the substrate W. In one embodiment, the measurement module PM5 includes a stage for mounting the substrate W, an imaging device, an illumination device, and an imaging unit including various sensors (temperature sensor, reflectivity measurement sensor, etc.). The imaging device may be, for example, a CCD camera for photographing the appearance of the substrate W. Alternatively, the imaging device may be a hyperspectral camera that splits light according to each wavelength and photographs it. The hyperspectral camera can measure any one or more of the pattern shape, size, film thickness, composition, and film density of the resist film.

[0163] In the developing module PM6, a developing process is performed on the substrate W. In one embodiment, the developing module PM6 includes a dry developing unit for performing dry developing on the substrate W. The dry developing unit may be, for example, a thermal processing device 100 (see Figure 1A ) or plasma processing device 1 (refer to Figure 2 and Figure 3 ).

[0164] In the third heat treatment module PM7, heat treatment is performed on the substrate W. In one embodiment, the third heat treatment module PM7 includes any one or more of a post-baking (Post Bake: PB) unit for heating the developed substrate W, a temperature adjustment unit for adjusting the temperature of the substrate W, and a high-precision temperature adjustment unit for adjusting the temperature of the substrate W with high precision. Each of these units may have one or more heat treatment devices. In one example, a plurality of heat treatment devices may be stacked. The heat treatment device may be, for example, the heat treatment device 100 (see Figure 1A ). Each heat treatment can be performed at a predetermined temperature using a predetermined gas.

[0165] The second carrier station CS2 carries in and carries out the second carrier C2 between the second carrier station CS2 and an external system of the substrate processing system SS. The structure and function of the second carrier station CS2 may be the same as those of the first carrier station CS1.

[0166] The control unit CT controls each structure of the substrate processing system SS to perform a given process on the substrate W. The control unit CT stores a recipe that sets a process sequence, process conditions, transport conditions, etc., and controls each structure of the substrate processing system SS according to the recipe to perform a given process on the substrate W. The control unit CT can have various control units ( Figures 1A to 4 The control unit 200, the control unit 200 and the control unit 400 shown in the figure may perform part or all of the functions.

[0167] <An Example of Substrate Processing Method>

[0168] Fig.18 1 is a flow chart showing a substrate processing method (hereinafter also referred to as "method MT") according to an exemplary embodiment. Fig.18 As shown, method MT includes: step ST100 of pre-treating a substrate, step ST200 of forming a resist film on a substrate, step ST300 of performing heat treatment (pre-baking: PAB) on the substrate with the resist film formed thereon, step ST400 of performing EUV exposure on the substrate, step ST500 of performing heat treatment on the exposed substrate (post-exposure baking: PEB), step ST600 of measuring the substrate, step ST700 of developing the resist film on the substrate, step ST800 of performing heat treatment on the developed substrate (post-baking: PB), and step ST900 of etching the substrate. Method MT may not include one or more of the above-mentioned steps. For example, method MT may not include step ST600, and step ST700 may be performed after step ST500.

[0169] Methods MT can use Fig.17Hereinafter, a case where the control unit CT of the substrate processing system SS controls each part of the substrate processing system SS and executes the method MT on the substrate W will be described as an example.

[0170] (Process ST100: Pre-processing)

[0171] First, a first carrier C1 containing a plurality of substrates W is moved into the first carrier station CS1 of the substrate processing system SS. The first carrier C1 is placed on the first loading plate ST1. Then, the first conveying device HD1 sequentially takes out each substrate W in the first carrier C1 and transfers it to the second conveying device HD2 of the first processing station PS1. The substrate W is conveyed to the pre-processing module PM1 by the second conveying device HD2. The substrate W is pre-processed by the pre-processing module PM1. The pre-processing may include, for example, one or more of the temperature adjustment of the substrate W, the formation of a part or all of the bottom film of the substrate W, the heating treatment of the substrate W, and the high-precision temperature adjustment of the substrate W. The pre-processing may include the surface modification treatment of the substrate W.

[0172] (Step ST200: Resist Film Formation)

[0173] Next, the substrate W is transported to the resist film forming module PM2 by the second transport device HD2. A resist film is formed on the substrate W by the resist film forming module PM2. In one embodiment, the formation of the resist film is performed by a wet process. For example, a resist film is formed by spin coating a resist film on the substrate W using a wet coating unit of the resist film forming module PM2. In one embodiment, a resist film is formed on the substrate W by a dry process such as a vapor deposition method. For example, a resist film is formed by evaporating a resist film on the substrate W using a dry coating unit of the resist film forming module PM2.

[0174] In addition, the resist film may be formed on the substrate W using both a dry process and a wet process. For example, after a first resist film is formed on the substrate W using a dry process, a second resist film may be formed on the first resist film using a wet process. In this case, the film thickness, material, and / or composition of the first resist film and the second resist film may be the same or different.

[0175] (Process ST300: PAB)

[0176] Next, the substrate W is transported to the first thermal treatment module PM3 by the second transport device HD2. The first thermal treatment module PM3 performs a heat treatment (pre-baking: PAB) on the substrate W. Pre-baking can be performed in an atmospheric environment or in an inert atmosphere. In addition, pre-baking can be performed by heating the substrate W to above 50°C or above 80°C. The heating temperature of the substrate W can be below 250°C, below 200°C, or below 150°C. In one example, the heating temperature of the substrate can be above 50°C and below 250°C. When a resist film is formed by a dry process in step ST200, in one embodiment, pre-baking can be continuously performed in a dry coating unit that performs step ST200. In one embodiment, after pre-baking, a process for removing the resist film at the end of the substrate W (Edge Bead Removal: EBR) can be performed.

[0177] (Process ST400: EUV exposure)

[0178] Next, the substrate W is transferred from the second transport device HD2 to the third transport device HD3 of the first interface station IS1. Then, the substrate W is transported to the exposure device EX by the third transport device HD3. The substrate W is exposed to EUV via an exposure mask (photomask) in the exposure device EX. Thus, on the substrate W, a first region exposed to EUV and a second region not exposed to EUV are formed corresponding to the pattern of the exposure mask (photomask).

[0179] (Process ST500: PEB)

[0180] 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. Then, the substrate W is transported to the second thermal processing module PM4 by the fifth transport device HD5. Then, a heat treatment (post-exposure baking: PEB) is performed on the substrate W in the second thermal processing module PM4. The post-exposure baking can be performed in an atmospheric environment. In addition, the post-exposure baking can be performed by heating the substrate W to a temperature of 180° C. or higher and 250° C. or lower.

[0181] (Process ST600: Measurement)

[0182] 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 other measurement. In one embodiment, the measurement of the measurement module PM5 includes measuring the appearance and / or size of the substrate W using a CCD camera. In one embodiment, the measurement of the measurement module PM5 includes measuring any one or more of the pattern shape, size, film thickness, composition, and film density of the resist film (hereinafter also referred to as "pattern shape, etc.") using a hyperspectral camera.

[0183] In one embodiment, the control unit CT determines whether the substrate W has exposure abnormality based on the measured appearance, size and / or pattern shape of the substrate W. In one embodiment, when the control unit CT determines that there is an exposure abnormality, the substrate W may be reprocessed or discarded without performing the development of step ST700. The reprocessing of the substrate W may be performed by removing the resist on the substrate W and returning to step ST200 to form a resist film. Reprocessing after development is sometimes accompanied by damage to the substrate W, but by performing reprocessing before development, damage to the substrate W can be avoided or suppressed.

[0184] (Process ST700: Development)

[0185] 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 developing process can be performed by dry developing. The developing process in step ST700 can be performed by the present processing method (see Figure 4 and Fig.13 ). After the development process or during the development process, one or more desorption processes may be performed. The desorption process includes removing scum or smoothing the surface of the resist film by an inert gas such as helium or a plasma of the inert gas. In addition, in the development process module PM6, after the development process, the developed resist film may be used as a mask to etch a portion of the base film.

[0186] (Process ST800: PB)

[0187] Next, the substrate W is transported to the third heat treatment module PM7 by the fifth transport device HD5, and a heating treatment (post-baking) is performed. Post-baking can be performed in an atmospheric environment or in a reduced pressure environment containing N2 or O2. In addition, post-baking can be performed by heating the substrate W to a temperature above 150°C and below 250°C. Post-baking can be performed by the second heat treatment module PM4 instead of the third heat treatment module PM7. In one embodiment, after post-baking, the substrate W can be optically measured by the measurement module PM5. The measurement involved can be performed in addition to the measurement in step ST600 or in place of the measurement in step ST600. In one embodiment, the control unit CT determines whether the development pattern of the substrate W has defects, scars, foreign matter adhesion, and other abnormalities based on the measured appearance, size, and / or pattern shape of the substrate W. In one embodiment, when it is determined in the control unit CT that an abnormality exists, the substrate W can be reprocessed or discarded without etching based on step ST900. In one embodiment, when the control unit CT determines that an abnormality exists, the opening size of the resist film on the substrate W may be adjusted using a dry coating unit (CVD device, ALD device, etc.).

[0188] (Process ST900: Etching)

[0189] After executing step ST800, the substrate W is transferred to the sixth transport device HD6 of the second carrier station CS2 by the fifth transport device HD5, and is transported to the second carrier C2 on the second carrier plate ST2 by the sixth transport device HD6. Then, the second carrier C2 is transported to a plasma processing system (not shown). The plasma processing system may be, for example, Figure 2 and Figure 3 The plasma processing system shown. In the plasma processing system, the developed resist film is used as a mask to etch the bottom film UF of the substrate W. Thus, the method MT ends. In addition, in step ST700, when the resist film is developed using a plasma processing device, the etching can be continued in the plasma processing chamber of the plasma processing device. In addition, when the second processing station PS2 is equipped with a plasma processing module in addition to the developing module PM6, the etching can also be performed in the plasma processing module. The above-mentioned desorption process can be performed more than once before or during etching.

[0190] The embodiments of the present disclosure also include the following aspects.

[0191] (Note 1)

[0192] A substrate processing method, comprising:

[0193] (a) providing a substrate having a base film and a metal-containing resist film formed on the base film on a substrate support portion in a chamber, the metal-containing resist film having an exposed first region and an unexposed second region; and

[0194] (b) supplying a processing gas to the chamber to develop the substrate and selectively remove the second region from the metal-containing resist film,

[0195] The step (b) comprises:

[0196] (b1) a step of controlling the temperature of the substrate or the substrate support portion to a first temperature to perform development; and

[0197] (b2) A step of controlling the temperature of the substrate or the substrate supporting portion to a second temperature different from the first temperature to perform development.

[0198] (Note 2)

[0199] The substrate processing method according to Supplement 1, wherein:

[0200] The second temperature is higher than the first temperature.

[0201] (Note 3)

[0202] The substrate processing method according to Supplement 1 or Supplement 2, wherein:

[0203] 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).

[0204] (Note 4)

[0205] A substrate processing method according to any one of Supplementary Notes 1 to 3, wherein:

[0206] The pressure in the chamber in the step (b2) is lower than the pressure in the chamber in the step (b1).

[0207] (Note 5)

[0208] A substrate processing method according to any one of Supplement 1 to Supplement 4, wherein:

[0209] The step (b) further includes a step of purging the processing gas in the chamber between the step (b1) and the step (b2).

[0210] (Note 6)

[0211] A substrate processing method according to any one of Supplementary Notes 1 to 5, wherein:

[0212] In the step (b1) and the step (b2), the processing gas is supplied to the chamber at a constant flow rate.

[0213] (Note 7)

[0214] A substrate processing method, comprising:

[0215] (a) providing a substrate having a base film and a metal-containing resist film formed on the base film on a substrate support portion in a chamber, the metal-containing resist film having an exposed first region and an unexposed second region; and

[0216] (b) supplying a processing gas to the chamber, developing the substrate, and selectively removing either the first region or the second region from the metal-containing resist film,

[0217] The step (b) comprises:

[0218] (b1) a step of developing the substrate under a first developing condition; and

[0219] (b2) a process of developing the substrate under a second developing condition different from the first developing condition, wherein at least one of the developing parameters of the second developing condition is different from that of the first developing condition, and the developing parameters include 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 relative to the substrate.

[0220] (Note 8)

[0221] The substrate processing method according to Supplement 7, wherein:

[0222] In the step (b), the development is performed using plasma generated from a processing gas, and the development parameters further include a power level of a source RF signal supplied to the chamber for generating plasma and a power or voltage level of a bias signal supplied to the chamber.

[0223] (Note 9)

[0224] The substrate processing method according to Supplementary Note 8, wherein:

[0225] The bias signal includes a bias RF signal or a voltage pulse,

[0226] The development parameters further include at least one of a frequency of the source RF signal, a frequency of the bias RF signal, and a frequency of the voltage pulse.

[0227] (Note 10)

[0228] The substrate processing method according to Supplement 8 or Supplement 9, wherein:

[0229] At least one of the source RF signal and the bias RF signal is pulsed, and the development parameters further include at least one of a duty cycle of the pulsed source RF signal and a duty cycle of the pulsed bias signal.

[0230] (Note 11)

[0231] A substrate processing method according to any one of Supplementary Notes 7 to 10, wherein:

[0232] In the step (b2), two or more of the development parameters of the second development condition are different from those of the first development condition.

[0233] (Note 12)

[0234] A substrate processing method according to any one of Supplementary Notes 1 to 11, wherein:

[0235] In the step (b), the steps (b1) and (b2) are repeated.

[0236] (Note 13)

[0237] A substrate processing method according to any one of Supplementary Notes 1 to 11, wherein:

[0238] In the step (b), after a cycle including the step (b1) and the step (b2) is performed once or more, the step (b1) is further performed.

[0239] (Note 14)

[0240] A substrate processing method according to any one of Supplementary Notes 1 to 11, wherein:

[0241] The process (b) includes performing one or more cycles of the process (b1) and the process (b2) without generating plasma from the processing gas, and then generating plasma from the processing gas and performing one or more cycles of the process (b1) and the process (b2).

[0242] (Note 15)

[0243] A substrate processing method according to any one of Supplementary Notes 1 to 11, wherein:

[0244] The process (b) includes generating plasma from the processing gas and performing a cycle including the process (b1) and the process (b2) one or more times, and then performing a cycle including the process (b1) and the process (b2) one or more times without generating plasma from the processing gas.

[0245] (Note 16)

[0246] A substrate processing method according to any one of Supplementary Notes 1 to 11, wherein:

[0247] In at least one of the step (b1) and the step (b2), the first region or the second region is selectively removed using plasma generated from the processing gas.

[0248] (Note 17)

[0249] A substrate processing method according to any one of Supplementary Notes 1 to 16, wherein:

[0250] The metal-containing resist film contains at least one metal selected from the group consisting of Sn, Hf, and Ti.

[0251] (Note 18)

[0252] A substrate processing method according to any one of Supplementary Notes 1 to 17, wherein:

[0253] The process gas includes a halogen-containing gas.

[0254] (Note 19)

[0255] A substrate processing method according to any one of Supplementary Notes 1 to 18, wherein:

[0256] The acidity of the processing gas used in the step (b1) is different from the acidity of the processing gas used in the step (b2).

[0257] (Note 20)

[0258] A substrate processing method according to any one of Supplementary Notes 1 to 19, wherein:

[0259] The substrate processing method further includes (c) after the step (b), etching the base film using the developed metal-containing film as a mask.

[0260] (Note 21)

[0261] The substrate processing method according to Supplementary Note 20, wherein:

[0262] The step (c) is performed in a chamber different from the chamber used in the step (b).

[0263] (Note 22)

[0264] The substrate processing method according to Supplementary Note 20, wherein:

[0265] The step (c) is performed in the chamber used in the step (b).

[0266] (Note 23)

[0267] A substrate processing method according to any one of Supplementary Notes 1 to 22, wherein:

[0268] The first region is exposed by EUV.

[0269] (Note 24)

[0270] A substrate processing method according to any one of Supplementary Notes 1 to 23, wherein:

[0271] The temperature of the substrate or the substrate support portion is controlled by at least one selected from the group consisting of the output of a heater within the substrate support portion, the output of a heater within a side wall of a chamber that accommodates the substrate support portion, the output of a heater within a top of the chamber, the temperature of a heat transfer fluid flowing within the substrate support portion, the pressure of a heat transfer gas supplied between the back side of the substrate and the surface of the substrate support portion, and the output of an electromagnetic wave configured to irradiate the surface of the substrate.

[0272] (Note 25)

[0273] A substrate processing system includes a substrate processing device and a control unit, wherein the substrate processing device includes a chamber, and the control unit is configured to perform the following control on the substrate processing device:

[0274] (a) providing a substrate having a base film and a metal-containing resist film formed on the base film on a substrate support portion in a chamber, the metal-containing resist film having an exposed first region and an unexposed second region; and

[0275] (b) supplying a processing gas to the chamber to develop the substrate and selectively remove the second region from the metal-containing resist film,

[0276] The control of (b) includes:

[0277] (b1) controlling the temperature of the substrate or the substrate support portion to a first temperature to perform development control; and

[0278] (b2) Controlling the development by controlling the temperature of the substrate or the substrate supporting portion to a second temperature different from the first temperature.

[0279] (Note 26)

[0280] A substrate processing system includes a substrate processing device and a control unit, wherein the substrate processing device includes a chamber, and the control unit is configured to perform the following control on the substrate processing device:

[0281] (a) providing a substrate having a base film and a metal-containing resist film formed on the base film on a substrate support portion in a chamber, the metal-containing resist film having an exposed first region and an unexposed second region; and

[0282] (b) supplying a processing gas to the chamber, developing the substrate, and selectively removing either the first region or the second region from the metal-containing resist film;

[0283] The control of (b) includes:

[0284] (b1) controlling development of the substrate under a first development condition; and

[0285] (b2) controlling the development of the substrate under a second development condition different from the first development condition, wherein at least one of the development parameters of the second development condition is different from that of the first development condition, and the development parameters include 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 relative to the substrate.

[0286] (Note 27)

[0287] A method for manufacturing a device, comprising:

[0288] (a) providing a substrate having a base film and a metal-containing resist film formed on the base film on a substrate support portion in a chamber, the metal-containing resist film having an exposed first region and an unexposed second region; and

[0289] (b) supplying a processing gas to the chamber to develop the substrate and selectively remove the second region from the metal-containing resist film,

[0290] The step (b) comprises:

[0291] (b1) a step of controlling the temperature of the substrate or the substrate support portion to a first temperature to perform development; and

[0292] (b2) A step of controlling the temperature of the substrate or the substrate supporting portion to a second temperature different from the first temperature to perform development.

[0293] (Note 28)

[0294] A method for manufacturing a device, comprising:

[0295] (a) providing a substrate having a base film and a metal-containing resist film formed on the base film on a substrate support portion in a chamber, the metal-containing resist film having an exposed first region and an unexposed second region; and

[0296] (b) supplying a processing gas to the chamber, developing the substrate, and selectively removing either the first region or the second region from the metal-containing resist film,

[0297] The step (b) comprises:

[0298] (b1) a step of developing the substrate under a first developing condition; and

[0299] (b2) a process of developing the substrate under a second developing condition different from the first developing condition, wherein at least one of the developing parameters of the second developing condition is different from that of the first developing condition, and the developing parameters include 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 relative to the substrate.

[0300] (Note 29)

[0301] A program that causes a computer of a substrate processing system having one or more substrate processing devices and a control unit to execute the following control:

[0302] (a) providing a substrate having a base film and a metal-containing resist film formed on the base film on a substrate support portion in a chamber, the metal-containing resist film having an exposed first region and an unexposed second region; and

[0303] (b) supplying a processing gas to the chamber to develop the substrate and selectively remove the second region from the metal-containing resist film,

[0304] The control of (b) includes:

[0305] (b1) controlling the temperature of the substrate or the substrate support portion to a first temperature to perform development control; and

[0306] (b2) Controlling the development by controlling the temperature of the substrate or the substrate supporting portion to a second temperature different from the first temperature.

[0307] (Note 30)

[0308] A program that causes a computer of a substrate processing system having one or more substrate processing devices and a control unit to execute the following control:

[0309] (a) providing a substrate having a base film and a metal-containing resist film formed on the base film on a substrate support portion in a chamber, the metal-containing resist film having an exposed first region and an unexposed second region; and

[0310] (b) supplying a processing gas to the chamber, developing the substrate, and selectively removing either the first region or the second region from the metal-containing resist film;

[0311] The control of (b) includes:

[0312] (b1) controlling development of the substrate under a first development condition; and

[0313] (b2) controlling the development of the substrate under a second development condition that is different from the first development condition, wherein at least one of the development parameters of the second development condition is different from that of the first development condition, and the development parameters include 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 relative to the substrate.

[0314] (Note 31)

[0315] A storage medium storing the program described in Supplement 29 or Supplement 30.

[0316] The above embodiments are described for the purpose of explanation and are not intended to limit the scope of the present disclosure. Various modifications can be made to the embodiments without departing from the scope and purpose of the present disclosure. For example, a part of the constituent elements in a certain embodiment can be added to other embodiments. In addition, a part of the constituent elements in a certain embodiment can be replaced with the corresponding constituent elements of other embodiments.

Claims

1. A substrate processing method, comprising: (a) providing a substrate having a base film and a metal-containing resist film formed on the base film on a substrate support portion in a chamber, wherein the metal-containing resist film has a first area to be exposed and a second area to be unexposed; and (b) supplying a processing gas to the chamber to develop the substrate and selectively remove the second region from the metal-containing resist film, The step (b) comprises: (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 supporting portion to a second temperature different from the first temperature to perform development.

2. The substrate processing method according to claim 1, wherein: The second temperature is higher than the first temperature.

3. The substrate processing method according to claim 1 or claim 2, wherein: In the step (b2), no processing gas is supplied to the chamber, or the flow rate of the processing gas supplied to the chamber is smaller than the flow rate of the processing gas supplied to the chamber in the step (b1).

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

5. The substrate processing method according to claim 1 or claim 2, wherein: The step (b) further includes a step of purging the processing gas in the chamber between the step (b1) and the step (b2).

6. The substrate processing method according to claim 1 or claim 2, wherein: In the step (b1) and the step (b2), the processing gas is supplied to the chamber at a constant flow rate.

7. A substrate processing method, comprising: (a) providing a substrate having a base film and a metal-containing resist film formed on the base film on a substrate support portion in a chamber, wherein the metal-containing resist film has a first area to be exposed and a second area to be unexposed; and (b) supplying a processing gas to the chamber, developing the substrate, and selectively removing either the first region or the second region from the metal-containing resist film, The step (b) comprises: (b1) developing the substrate under a first developing condition; and (b2) a process of developing the substrate under a second developing condition different from the first developing condition, wherein at least one of the developing parameters of the second developing condition is different from that of the first developing condition, and the developing parameters include 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 relative to the substrate.

8. The substrate processing method according to claim 7, wherein: In the step (b), the development is performed using plasma generated by the processing gas, and the development parameters further include a power level of a source RF signal supplied to the chamber for generating plasma and a power or voltage level of a bias signal supplied to the chamber.

9. The substrate processing method according to claim 8, wherein: The bias signal includes a bias radio frequency signal or a voltage pulse, The development parameters further include at least one of a frequency of the source RF signal, a frequency of the bias RF signal, and a frequency of the voltage pulse.

10. The substrate processing method according to claim 8, wherein: At least one of the source RF signal and the bias RF signal is pulsed, and the development parameters further include at least one of a duty cycle of the pulsed source RF signal and a duty cycle of the pulsed bias signal.

11. The substrate processing method according to any one of claims 7 to 10, wherein: In the step (b2), two or more of the development parameters of the second development condition are different from those of the first development condition.

12. The substrate processing method according to claim 1 or claim 7, wherein: In the step (b), the steps (b1) and (b2) are repeated.

13. The substrate processing method according to claim 1 or claim 7, wherein: In the step (b), after a cycle including the step (b1) and the step (b2) is performed once or more, the step (b1) is further performed.

14. The substrate processing method according to claim 1 or claim 7, wherein: The process (b) includes performing one or more cycles of the process (b1) and the process (b2) without generating plasma from the processing gas, and then generating plasma from the processing gas and performing one or more cycles of the process (b1) and the process (b2).

15. The substrate processing method according to claim 1 or claim 7, wherein: The process (b) includes generating plasma from the processing gas and performing a cycle including the process (b1) and the process (b2) one or more times, and then performing a cycle including the process (b1) and the process (b2) one or more times without generating plasma from the processing gas.

16. The substrate processing method according to claim 1 or claim 7, wherein: In at least one of the step (b1) and the step (b2), the first region or the second region is selectively removed using plasma generated from the processing gas.

17. The substrate processing method according to claim 1 or claim 7, wherein: The metal-containing resist film contains at least one metal selected from the group consisting of Sn, Hf, and Ti.

18. The substrate processing method according to claim 1 or claim 7, wherein: The process gas includes a halogen-containing gas.

19. The substrate processing method according to claim 1 or claim 7, wherein: The acidity of the processing gas used in the step (b1) is different from the acidity of the processing gas used in the step (b2).

20. The substrate processing method according to claim 1 or claim 7, wherein: The substrate processing method further includes: (c) after the step (b), a step of etching the base film using the developed metal-containing film as a mask.

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

22. The substrate processing method according to claim 20, wherein: The step (c) is performed in the chamber used in the step (b).

23. The substrate processing method according to claim 1 or claim 7, wherein: The first region is exposed by EUV.

24. The substrate processing method according to claim 1 or claim 7, wherein: The temperature of the substrate or the substrate support portion is controlled by at least one selected from the group consisting of the output of a heater within the substrate support portion, the output of a heater within a side wall of a chamber that accommodates the substrate support portion, the output of a heater within a top of the chamber, the temperature of a heat transfer fluid flowing within the substrate support portion, the pressure of a heat transfer gas supplied between the back side of the substrate and the surface of the substrate support portion, and the output of an electromagnetic wave configured to irradiate the surface of the substrate.

25. A substrate processing system comprising a substrate processing device and a control unit, wherein the substrate processing device has a chamber, and the control unit is configured to perform the following control on the substrate processing device: (a) providing a substrate having a base film and a metal-containing resist film formed on the base film on a substrate support portion in a chamber, wherein the metal-containing resist film has a first area to be exposed and a second area to be unexposed; and (b) supplying a processing gas to the chamber to develop the substrate and selectively remove the second region from the metal-containing resist film, The control of (b) includes: (b1) controlling the temperature of the substrate or the substrate support portion to a first temperature to control the development; and (b2) Controlling the development by controlling the temperature of the substrate or the substrate supporting portion to a second temperature different from the first temperature.

26. A substrate processing system comprising a substrate processing device and a control unit, wherein the substrate processing device has a chamber, and the control unit is configured to perform the following control on the substrate processing device: (a) providing a substrate having a base film and a metal-containing resist film formed on the base film on a substrate support portion in a chamber, wherein the metal-containing resist film has a first area to be exposed and a second area to be unexposed; and (b) supplying a processing gas to the chamber, developing the substrate, and selectively removing either the first region or the second region from the metal-containing resist film; The control of (b) includes: (b1) controlling the development of the substrate under a first development condition; and (b2) controlling the development of the substrate under a second development condition that is different from the first development condition, wherein at least one of the development parameters of the second development condition is different from that of the first development condition, and the development parameters include 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 relative to the substrate.

Images