Substrate processing method, composition for forming metal-containing resist, metal-containing resist, and substrate processing system

Abstract

A substrate processing method is provided. The method comprises: (a) a step for providing a substrate having a base film; and (b) a step for forming a metal-containing resist film on the base film using a metal-containing precursor having a photosensitive group and a polyfunctional compound.

Description

Technical Field

[0001] Exemplary embodiments of the present disclosure relate to a substrate processing method, a composition for forming a metal-containing resist, a metal-containing resist, and a substrate processing system. Background Art

[0002] Patent Document 1 discloses a technique for forming a patterning film on a semiconductor substrate using extreme ultraviolet light (hereinafter referred to as "EUV light").

[0003] Prior Art Documents

[0004] Patent Documents

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

[0006] The present disclosure provides a technique for adjusting the composition of a metal-containing resist film formed on a substrate.

[0007] In one exemplary embodiment of the present disclosure, there is provided a substrate processing method having: (a) a step of providing a substrate having an underlayer film; and (b) a step of forming a metal-containing resist film on the underlayer film using a metal precursor having a photosensitive group and a polyfunctional compound.

[0008] Advantages of the Invention

[0009] According to one exemplary embodiment of the present disclosure, a technique for adjusting the composition of a metal-containing resist film formed on a substrate can be provided. Brief Description of the Drawings

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

[0011] Figure 2 is a diagram for explaining a structural example of a plasma processing system.

[0012] Figure 3 is a diagram for explaining a structural example of a capacitively coupled plasma processing apparatus.

[0013] Figure 4 is a diagram for explaining a structural example of a liquid processing system.

[0014] Figure 5 is a flowchart showing the present processing method.

[0015] Figure 6 is a diagram showing an example of an underlayer film UF of a substrate W.

[0016] Figure 7It is a diagram showing an example of the underfilm UF of the substrate W.

[0017] Figure 8 It is a diagram showing an example of the cross-sectional structure of the substrate W on which the metal-containing resist film RM is formed.

[0018] Figure 9 It is a flowchart showing an example of the process ST2 using the ALD method.

[0019] Figure 10 It is a flowchart showing an example of the process ST2 using the ALD method.

[0020] Figure 11 It is a diagram schematically showing an example of the phenomenon generated on the surface of the substrate W in the process ST2 using the ALD method.

[0021] Figure 12 It is a block diagram for explaining an example of the structure of the substrate processing system SS.

[0022] Figure 13 It is a flowchart showing the method MT.

[0023] Explanation of reference numerals

[0024] 1... Plasma processing apparatus; 2... Control unit; 10... Plasma processing chamber; 11... Substrate support part; 20... Gas supply part; 30... Power supply; 100... Heat treatment apparatus; 102... Processing chamber; 120... Stage heater; 121... Substrate support part; 141... Gas nozzle; 200... Control unit; 300... Liquid processing apparatus; 311... Rotating chuck; 321... Cup; 331... Processing liquid supply nozzle; 351... Cleaning liquid supply nozzle; 400... Control unit; RM... Metal-containing resist film; UF... Underfilm; W... Substrate. Detailed description of the embodiments

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

[0026] In one exemplary embodiment, a substrate processing method is provided, which has: (a) a step of providing a substrate having an underfilm; and (b) a step of forming a metal-containing resist film on the underfilm using a metal-containing precursor having a photosensitive group and a polyfunctional compound.

[0027] In one exemplary embodiment, the metal-containing precursor contains a compound (α) having an amino group and / or an alkoxy group.

[0028] In one exemplary embodiment, the compound (α) contains a compound (α1), and the compound (α1) contains at least one metal selected from the group consisting of Sn, Ti, Hf, Zr, and In.

[0029] In one exemplary embodiment, the compound (α1) contains Sn.

[0030] In one exemplary embodiment, the photosensitive group contains at least one group selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, and -CH x F y (where x represents an integer from 0 to 2 and y represents an integer from 1 to 3).

[0031] In one exemplary embodiment, the polyfunctional compound contains at least one compound (β) selected from the group consisting of polyols, polythiols, polycarboxylic acids, polyisocyanates, and polyisothiocyanates.

[0032] In one exemplary embodiment, in the step (b), at least one selected from the group consisting of H 2 O, H 2 O 2 、O 3 and O 2 is further used.

[0033] In one exemplary embodiment, the step (b) includes: (b1) a step of supplying a gas containing a metal precursor onto a bottom film to form a metal precursor film; and (b2) a step of supplying a gas containing a polyfunctional compound onto the metal precursor film to form a metal-containing resist film from the metal precursor film.

[0034] In one exemplary embodiment, the steps of (b1) and (b2) are repeated multiple times.

[0035] In one exemplary embodiment, the step (b) includes using a mixed gas containing a metal precursor and a polyfunctional compound to form a metal-containing resist film.

[0036] In one exemplary embodiment, the metal precursor contains a metal complex, and the metal complex contains at least one metal selected from the group consisting of Sn, Ti, Hf, Zr, and In.

[0037] In one exemplary embodiment, the polyfunctional compound contains at least one compound (β) selected from the group consisting of polyols, polythiols, polycarboxylic acids, polyisocyanates, and polyisothiocyanates.

[0038] In one exemplary embodiment, the step (b) includes a step of coating a solution containing a metal precursor and a polyfunctional compound on a bottom film and a step of heating the coated solution to form a metal-containing resist film.

[0039] In an exemplary embodiment, the substrate processing method further includes: (c) after the step of (b), exposing the substrate and forming an exposed first region and an unexposed second region in the metal-containing resist film; and (d) developing the substrate and selectively removing the second region from the metal-containing resist film.

[0040] In an exemplary embodiment, in the step of (d), the second region is removed by a developing gas or a developer containing a weak acid.

[0041] In an exemplary embodiment, the weak acid includes an organic acid having a pKa of less than 16.

[0042] In an exemplary embodiment, the organic acid includes at least one selected from the group consisting of alcohols, thiols, carboxylic acids, sulfonic acids, β-diketones, alkyl carbonates, and azoles.

[0043] In an exemplary embodiment, there is provided a composition for forming a metal-containing resist, including: a metal-containing precursor having a photosensitive group and a polyfunctional compound, the metal-containing precursor including a compound having a photosensitive group, an amino group, and / or an alkoxy group.

[0044] In an exemplary embodiment, there is provided a metal-containing resist including a compound having a repeating unit represented by the following formula (1) in the molecule:

[0045] -(M-X-A-X)-(1)

[0046] (In the above formula (1), M represents Sn, Ti, Hf, Zr, or In, X represents a divalent group derived from a terminal functional group of a polyol, a polythiol, a polycarboxylic acid, a polyisocyanate, or a polyisothiocyanate, and A represents a divalent organic group having 2 or more and 10 or less carbon atoms).

[0047] In an exemplary embodiment, there is provided a substrate processing system having one or more substrate processing apparatuses and a control unit, the control unit being configured to perform the following controls on the one or more substrate processing apparatuses: (a) control for providing a substrate having an underlayer film; and (b) control for forming a metal-containing resist film on the underlayer film using a metal-containing precursor having a photosensitive group and a polyfunctional compound.

[0048] In an exemplary embodiment, a development method is provided. The development method includes: (a) a step of providing a substrate having a bottom film and a metal-containing resist on the bottom film; (b) a step of exposing the metal-containing resist via an exposure mask to form an exposed first region and an unexposed second region in the metal-containing resist; and (c) a step of selectively removing one of the first region and the second region. The metal-containing resist in (a) contains a compound having a repeating unit represented by the following formula (1) in the molecule:

[0049] -(M-X-A-X)-(1)

[0050] (In the above formula (1), M represents Sn, Ti, Hf, Zr or In, X represents a divalent group derived from the terminal functional group of a polyol, a polythiol, a polycarboxylic acid, a polyisocyanate or a polyisothiocyanate, and A represents a divalent organic group having 2 or more and 10 or less carbon atoms).

[0051] In an exemplary embodiment, an etching method is provided. The etching method includes: (a) a step of providing a substrate having a bottom film and a metal-containing resist on the bottom film, wherein the metal-containing resist has at least one opening; (b) a step of etching the bottom film via the opening. The metal-containing resist contains a compound having a repeating unit represented by the following formula (1) in the molecule:

[0052] -(M-X-A-X)- (1)

[0053] (In the above formula (1), M represents Sn, Ti, Hf, Zr or In, X represents a divalent group derived from the terminal functional group of a polyol, a polythiol, a polycarboxylic acid, a polyisocyanate or a polyisothiocyanate, and A represents a divalent organic group having 2 or more and 10 or less carbon atoms).

[0054] Hereinafter, each embodiment of the present disclosure will be described in detail with reference to the drawings. In addition, the same or similar elements are denoted by the same reference numerals in the respective drawings, and repeated description is omitted. Unless otherwise specified, the positional relationships such as up, down, left and right are described based on the positional relationships shown in the drawings. The dimensional ratios of the drawings do not represent actual ratios, and the actual ratios are not limited to the ratios shown in the drawings.

[0055] The substrate processing method according to the present disclosure can be executed by a substrate processing system. In one embodiment, the substrate processing system is a substrate processing system having one or more substrate processing apparatuses and a control unit, and the control unit is configured to execute the following controls on the one or more substrate processing apparatuses: (a) control for providing a substrate having a bottom film; and (b) control for forming a metal-containing resist film on the bottom film using a metal-containing precursor having a photosensitive group and a polyfunctional compound. The substrate processing system according to the present disclosure may include a heat treatment system, a plasma processing system, a liquid processing system, and the like.

[0056] <Configuration example of heat treatment system>

[0057] Figure 1 This 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 processing system, and the heat treatment apparatus 100 is an example of a substrate processing apparatus.

[0058] The heat treatment apparatus 100 has a processing chamber 102 configured to form a sealed space. The processing chamber 102 is, for example, an airtight cylindrical container configured to adjust the ambient gas inside. 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.

[0059] A substrate support portion 121 is provided on the lower side inside the processing chamber 102. The substrate support portion 121 has a substrate support surface for supporting the substrate W thereon. The substrate support portion 121 is, for example, circular in plan view, and the substrate W is placed on its horizontally formed surface (upper surface). A stage heater 120 is buried 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) may be arranged around the substrate W on the substrate support portion 121. The ring assembly may include one or more annular members. By arranging the ring assembly around the substrate W, the temperature controllability of the outer peripheral region of the substrate W can be improved. Depending on the heat treatment as the purpose, the ring assembly may be made of an inorganic material or an organic material.

[0060] The substrate support portion 121 is supported within the processing chamber 102 by columns 122 provided on the bottom surface of the processing chamber 102. A plurality of lift pins 123 that can vertically move up and down are provided on the outer circumferential side of the columns 122. The plurality of lift pins 123 are respectively inserted through through-holes provided in the substrate support portion 121. The plurality of lift pins 123 are arranged at intervals in the circumferential direction. The lifting operation of the plurality of lift pins 123 is controlled by a lifting mechanism 124. When the lift pins 123 project toward the surface of the substrate support portion 121, the substrate W can be transferred between a transfer mechanism (not shown) and the substrate support portion 121.

[0061] An exhaust port 131 having an opening is provided in the side wall of the processing chamber 102. The exhaust port 131 is connected to an exhaust mechanism 132 via an exhaust pipe. The exhaust mechanism 132 is composed of a vacuum pump, a valve, etc., and adjusts the exhaust flow rate from the exhaust port 131. By adjusting the exhaust flow rate, etc. by this exhaust mechanism 132, the pressure inside the processing chamber 102 is adjusted. In addition, on the side wall of the processing chamber 102, at a position different from the position where the exhaust port 131 is opened, a transfer port for the substrate W (not shown) is formed so as to be freely opened and closed.

[0062] 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 for the substrate W. The gas nozzle 141 supplies a processing gas into the processing chamber 102. When viewed from the central portion of the substrate support portion 121, 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. That is, the gas nozzle 141 is symmetrically provided on the side wall of the processing chamber 102 with respect to a vertical virtual plane passing through the central portion of the substrate support portion 121 and the exhaust port 131.

[0063] The gas nozzle 141 is formed in a rod shape that protrudes from the side wall of the processing chamber 102 toward the center side of the processing chamber 102. The front end portion of the gas nozzle 141 extends horizontally from the side wall of the processing chamber 102, for example. The processing gas is sprayed into the processing chamber 102 from a spray port opened at the front end of the gas nozzle 141 and flows along the Figure 1 arrow direction of the dotted line shown, and is exhausted from the exhaust port 131. In addition, the front end portion of the gas nozzle 41 may have a shape that extends obliquely downward toward the substrate W, or may have a shape that extends obliquely upward toward the top surface 140 of the processing chamber 102.

[0064] In addition, the gas nozzle 141 may be provided on the top wall of the processing chamber 102, for example. In addition, the exhaust port 131 may be provided on the bottom surface of the processing chamber 102.

[0065] 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 inside 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 for vaporizing a material in a liquid state.

[0066] The control unit 200 processes computer-executable instructions for causing the heat treatment apparatus 100 to perform various processes described in the present disclosure. The control unit 200 may be configured to control each element of the heat treatment apparatus 100 to perform various processes described herein. In one embodiment, part or all of the control unit 200 may be included in the heat treatment apparatus 100. The control unit 200 may include a processing unit 200a1, a storage unit 200a2, and a communication interface 200a3. The control unit 200 is implemented by a computer 200a, for example. 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 needed. The acquired program is stored in the storage unit 200a2 and read and executed by the processing unit 200a1 from the storage unit 200a2. 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), an HDD (Hard Disk Drive), an SSD (Solid State Drive), or a combination thereof. The communication interface 200a3 may also communicate with the heat treatment apparatus 100 via a communication circuit such as a LAN (Local Area Network).

[0067] <Configuration example of plasma processing system>

[0068] Figure 2It is a diagram for explaining a configuration example of a plasma processing system. In one embodiment, the plasma processing system includes a plasma processing apparatus 1 and a controller 2. The plasma processing system is an example of a substrate processing system, and the plasma processing apparatus 1 is an example of a substrate processing apparatus. The plasma processing apparatus 1 includes a plasma processing chamber (hereinafter simply referred to as "processing chamber") 10, a substrate support portion 11, and a plasma generation 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 discharge port for discharging gas from the plasma processing space. The gas supply port is connected to a gas supply portion 20 described later, and the gas discharge port is connected to an exhaust system 40 described later. The substrate support portion 11 is disposed in the plasma processing space and has a substrate support surface for supporting a substrate.

[0069] The plasma generation portion 12 is configured to generate plasma from at least one processing gas supplied into the plasma processing space. The plasma formed in the plasma processing space may be capacitive coupled plasma (CCP), inductive coupled plasma (ICP), ECR plasma (Electron-Cyclotron-Resonance Plasma), helicon wave plasma (HWP), or surface wave plasma (SWP), etc. In addition, various types of plasma generation portions including an alternating current (AC) plasma generation portion and a direct current (DC) plasma generation portion may also be used. In one embodiment, the alternating current signal (alternating current power) used in the AC plasma generation portion has a frequency in the range of 100 kHz to 10 GHz. Therefore, the alternating current signal includes a radio frequency (RF) signal and a microwave signal. In one embodiment, the RF signal has a frequency in the range of 100 kHz to 150 MHz.

[0070] 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 may be configured to control each element of the plasma processing apparatus 1 to perform the various processes described herein. In one embodiment, part or all of the control unit 2 may be included in the plasma processing apparatus 1. The control unit 2 is implemented by a computer 2a, for example. The control unit 2 may also include a processing unit 2a1, a storage unit 2a2, and a communication interface 2a3. Each structure of the control unit 2 may be the same as each structure of the above-described control unit 200 (see Figure 1 ).

[0071] Hereinafter, a configuration example of a capacitively coupled plasma processing apparatus as an example of the plasma processing apparatus 1 will be described. Figure 3 FIG. is a diagram for explaining a configuration example of a capacitively coupled plasma processing apparatus.

[0072] 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 showerhead 13. The substrate support unit 11 is disposed in the plasma processing chamber 10. The showerhead 13 is disposed above the substrate support unit 11. In one embodiment, the showerhead 13 forms at least a part of the ceiling of the plasma processing chamber 10. The plasma processing chamber 10 has a plasma processing space 10s defined by the showerhead 13, the sidewall 10a of the plasma processing chamber 10, and the substrate support unit 11. The plasma processing chamber 10 is grounded. The showerhead 13 and the substrate support unit 11 are electrically insulated from the housing of the plasma processing chamber 10.

[0073] The substrate support unit 11 includes a main body portion 111 and a ring assembly 112. The main body portion 111 has a central region 111a for supporting the substrate W and an annular region 111b for supporting the ring assembly 112. A wafer is an example of the substrate W. The annular region 111b of the main body portion 111 surrounds the central region 111a of the main body portion 111 in a plan view. The substrate W is disposed on the central region 111a of the main body portion 111, and the ring assembly 112 is disposed on the annular region 111b of the main body portion 111 so as to surround the substrate W on the central region 111a of the main body portion 111. Therefore, the central region 111a is also referred to as a substrate support surface for supporting the substrate W, and the annular region 111b is also referred to as a ring support surface for supporting the ring assembly 112.

[0074] 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 disposed on the base 1110. The electrostatic chuck 1111 includes a ceramic component 1111a and an electrostatic electrode 1111b disposed within the ceramic component 1111a. The ceramic component 1111a has a central region 111a. In one embodiment, the ceramic component 1111a further includes an annular region 111b. Additionally, other components surrounding the electrostatic chuck 1111, such as an annular electrostatic chuck or an annular insulating component, may also have the annular region 111b. In this case, the ring assembly 112 can be disposed on the annular electrostatic chuck or the annular insulating component, and can be disposed on both the electrostatic chuck 1111 and the annular insulating component simultaneously. Additionally, at least one RF / DC electrode connected to an RF power supply 31 and / or a DC power supply 32 described later can also be disposed within the ceramic component 1111a. In this case, the at least one RF / DC electrode functions as a lower electrode. When a bias RF signal and / or a DC signal described later are supplied to the at least one RF / DC electrode, the RF / DC electrode is also referred to as a bias electrode. Additionally, the conductive component of the base 1110 and the at least one RF / DC electrode can also function as a plurality of lower electrodes. Additionally, the electrostatic electrode 1111b can also function as a lower electrode. Therefore, the substrate support portion 11 includes at least one lower electrode.

[0075] The ring assembly 112 includes one or more annular components. In one embodiment, the one or more annular 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.

[0076] Additionally, the substrate support portion 11 may also include a temperature control module configured to adjust at least one of the electrostatic chuck 1111, the ring assembly 112, and the substrate to a target temperature. The temperature control module may include a heater, a heat transfer medium, a flow path 1110a, or a combination thereof. A heat transfer fluid such as brine or gas flows through the flow path 1110a. In one embodiment, the flow path 1110a is formed within the base 1110, and one or more heaters are disposed within the ceramic component 1111a of the electrostatic chuck 1111. Additionally, the substrate support portion 11 may also include a heat transfer gas supply portion configured to supply a heat transfer gas to a gap between the back surface of the substrate W and the central region 111a.

[0077] 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 one or more side gas injectors (SGI: Side Gas Injector) installed in one or more openings formed in the side wall 10a in addition to the showerhead 13.

[0078] The gas supply unit 20 may include at least one gas source 21 and at least one flow controller 22. In one embodiment, the gas supply unit 20 is configured to supply at least one processing gas to the showerhead 13 from the respective corresponding gas sources 21 via the respective corresponding flow controllers 22. Each flow controller 22 may include, for example, a mass flow controller or a pressure-controlled flow controller. Moreover, the gas supply unit 20 may include one or more flow modulation devices for modulating or pulsing the flow rate of at least one processing gas.

[0079] The power supply 30 includes a radio frequency power supply 31, and the radio frequency power supply 31 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. Thereby, a plasma is formed from 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 generation 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 component in the formed plasma can be introduced into the substrate W.

[0080] In one embodiment, the radio frequency power supply 31 includes a first radio frequency generation unit 31a and a second radio frequency generation unit 31b. The first radio frequency generation unit 31a is configured to be coupled to at least one lower electrode and / or at least one upper electrode via at least one impedance matching circuit, and generate a source radio frequency signal (source radio frequency power) for plasma generation. In one embodiment, the source radio frequency signal has a frequency in the range of 10 MHz to 150 MHz. In one embodiment, the first radio frequency generation unit 31a may also be configured to generate a plurality of source radio frequency signals having different frequencies. The generated one or more source radio frequency signals are supplied to at least one lower electrode and / or at least one upper electrode.

[0081] The second radio frequency generating unit 31b is configured to be coupled to at least one lower electrode via at least one impedance matching circuit to generate a bias radio frequency signal (bias radio frequency power). The frequency of the bias radio frequency signal may be the same as or different from the frequency of the source radio frequency signal. In one embodiment, the bias radio frequency signal has a frequency lower than the frequency of the source radio frequency signal. In one embodiment, the bias radio frequency signal has a frequency in the range of 100 kHz to 60 MHz. In one embodiment, the second radio frequency generating unit 31b may also be configured to generate a plurality of bias radio frequency signals having different frequencies. The one or more generated bias radio frequency signals are supplied to at least one lower electrode. Further, in various embodiments, at least one of the source radio frequency signal and the bias radio frequency signal may be pulsed.

[0082] 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.

[0083] 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. Further, the sequence of voltage pulses may include one or more positive polarity voltage pulses and one or more negative polarity voltage pulses within one cycle. Additionally, 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 in place of the second radio frequency generating unit 31b.

[0084] The exhaust system 40 may be connected, for example, to a gas discharge port 10e provided at the bottom of the plasma processing chamber 10. The exhaust system 40 may include a pressure regulating valve and a vacuum pump. The pressure in the plasma processing space 10s is regulated by the pressure regulating valve. The vacuum pump may include a turbo molecular pump, a dry pump, or a combination thereof.

[0085] <Configuration example of liquid processing system>

[0086] Figure 4 This is a diagram for explaining a configuration example of a liquid processing system. In one embodiment, the liquid processing system includes a liquid processing apparatus 300 and a control unit 400. The liquid processing system is an example of a substrate processing system, and the liquid processing apparatus 300 is an example of a substrate processing apparatus.

[0087] As Figure 4 shown, the liquid processing apparatus 300 has a rotating chuck 311 as a substrate support portion within a processing chamber 310. The rotating chuck 311 horizontally holds a substrate W. The rotating chuck 311 is connected to a rotatable portion 312 that is free to move up and down, and the rotatable portion 312 is connected to a rotation drive portion 313 composed of a motor or the like. By driving the rotation drive portion 313, the substrate W held on the rotating chuck 311 can rotate.

[0088] A cup 321 is disposed outside the rotating chuck 311 to prevent the processing liquid (such as resist liquid, developer liquid, cleaning liquid, etc.) or the liquid mist of the processing liquid from scattering around the cup 321. A drain pipe 323 and an exhaust pipe 324 are provided at the bottom 322 of the cup 321. The drain pipe 323 communicates with a drainage device 325 such as a drain pump. The exhaust pipe 324 communicates with an exhaust device 327 such as an exhaust pump via a valve 326.

[0089] Above the processing chamber 310 of the liquid processing apparatus 300, a blowing device 314 is provided that supplies air with a required temperature and humidity as downstream into the cup 321.

[0090] When forming a puddle of the processing liquid on the substrate W, a processing liquid supply nozzle 331 is used. The processing liquid supply nozzle 331 is provided on a nozzle support portion 332 such as an arm, for example. The nozzle support portion 332 is free to move up and down as indicated by the reciprocating arrow A shown by the dashed line in the figure, and is also free to move horizontally as indicated by the reciprocating arrow B shown by the dashed line. The processing liquid supply nozzle 331 supplies the processing liquid (such as resist liquid or developer liquid, etc.) from a processing liquid supply source 334 via a supply pipe 333.

[0091] When forming a liquid pit, in the case of using a so-called long-orifice nozzle having a length greater than the diameter of the substrate W, by scanning from one end to the other end on the substrate W, a liquid pit of the processing liquid can be formed on the substrate W. In addition, in the case of a so-called straight nozzle that ejects a liquid column with a width sufficiently smaller than the diameter of the substrate W, by positioning the ejection port above the center of the substrate W and ejecting the processing liquid while rotating the substrate W, the processing liquid can be diffused over the entire surface of the substrate W to form a liquid pit of the processing liquid on the substrate W. In addition, the formation of the liquid pit of the processing liquid can also be performed by scanning the straight nozzle on the substrate W in the same manner as the long-orifice nozzle, or by arranging ejection ports that eject liquid in a straight shape on a plurality of substrates W and supplying the processing liquid from each ejection port.

[0092] The gas nozzle 341 has a nozzle body 342. The nozzle body 342 is provided on a nozzle support portion such as an arm, and this nozzle support portion is vertically movable freely like the reciprocating arrow C shown by the dashed line in the figure, and is horizontally movable freely like the reciprocating arrow D shown by the dashed line.

[0093] The gas nozzle 341 has two nozzle ejection ports 343, 344. The nozzle ejection ports 343, 344 are formed by branching from the gas flow path 345. The gas flow path 345 leads to a gas supply source 347 via a gas supply pipe 346. In the gas supply source 347, nitrogen is prepared as an inert gas or a non-oxidizing gas, for example. When supplying nitrogen to the gas nozzle 341 from the gas flow path 345, nitrogen is ejected from each of the nozzle ejection ports 343, 344.

[0094] In addition, a cleaning liquid supply nozzle 351 for cleaning the processing liquid after liquid processing on the substrate W is provided on the gas nozzle 341. The cleaning liquid supply nozzle 351 communicates with a cleaning liquid supply source 353 via a cleaning liquid supply pipe 352. As the cleaning liquid, pure water is used, for example. The cleaning liquid supply nozzle 351 is located between the two nozzle ejection ports 343, 344, but its position is not limited thereto. The cleaning liquid supply nozzle 351 may also have a structure independent of the gas nozzle 341.

[0095] The control unit 400 processes computer-executable instructions for causing the liquid processing apparatus 300 to perform various processes described in the present disclosure. The control unit 400 can be configured to control each element of the liquid processing apparatus 300 to perform various processes described herein. In one embodiment, part or all of the control unit 400 may be included in the liquid processing apparatus 300. The control unit 400 is realized by a computer 400a, for example. The computer 400a may include a processing unit 400a1, a storage unit 400a2, and a communication interface 400a3. Each structure of the control unit 400 may be the same as each structure of the above-described control unit 200 (refer to Figure 1 ).

[0096] <Example of Substrate Processing Method>

[0097] Figure 5 It is a flowchart showing a substrate processing method (hereinafter also referred to as "this processing method") according to an exemplary embodiment. This processing method includes a step ST1 of providing a substrate having an underlayer film and a step ST2 of forming a metal-containing resist film on the underlayer film. In one embodiment, the formation process (hereinafter also referred to as "film formation process") of the metal-containing resist film in step ST2 is performed by a dry process (hereinafter also referred to as "dry film formation") using a processing gas. In one embodiment, the film formation process in step ST2 is performed by a wet process (hereinafter also referred to as "wet film formation") using a solution. In one embodiment, the film formation process in step ST2 is performed using both wet film formation and dry film formation.

[0098] This processing method can have: (a) a step of providing a substrate having an underlayer film (corresponding to "step ST1" described later); and (b) a step of forming a metal-containing resist film on the aforementioned underlayer film using a metal-containing precursor having a photosensitive group and a polyfunctional compound (corresponding to "step ST2" described later). Each step can be executed using any one of the above substrate processing systems (refer to Figures 1 to 4 ), and in addition, it can also be executed using two or more of these substrate processing systems. For example, this processing method can be executed in a heat treatment system (refer to Figure 1 ). Hereinafter, an example will be described in which the control unit 200 controls each part of the heat treatment apparatus 100 to perform this processing method on the substrate W.

[0099] (Step ST1: Providing a Substrate)

[0100] First, in step ST1, the substrate W is provided in the processing chamber 102 of the heat treatment apparatus 100. The substrate W is provided on the substrate support portion 121 via the lift pins 123. After the substrate W is disposed on the substrate support portion 121, the temperature of the substrate support portion 121 is adjusted to the set temperature. The set temperature can be, for example, a temperature of 350 °C or lower, or a temperature of 25 °C or higher and 350 °C or lower. The temperature adjustment of the substrate support portion 121 can be performed by controlling the output of one or more of 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 this processing method, the temperature of the substrate support portion 121 can be adjusted to the set temperature before step ST1. That is, after adjusting the temperature of the substrate support portion 121 to the set temperature, the substrate W can be provided to the substrate support portion 121.

[0101] The substrate W can be used to fabricate semiconductor devices. The semiconductor devices include, for example, semiconductor memory devices such as DRAM, 3D-NAND flash memories, and logic devices. The substrate W has a bottom film UF. The bottom film UF can be an organic film, a dielectric film, a metal film, or a semiconductor film formed on a silicon wafer, or a laminated film thereof. In one embodiment, the bottom film UF contains, for example, at least one selected from the group consisting of a silicon-containing film, a carbon-containing film, and a metal-containing film.

[0102] Figure 6 and Figure 7 are diagrams respectively showing an example of the bottom film UF of the substrate W. As Figure 6 shown, the bottom film UF can be composed of a first film UF1, a second film UF2, and a third film UF3. As Figure 7 shown, the bottom film UF can be composed of the second film UF2 and the third film UF3. In one embodiment, the surface of the bottom film UF can be modified.

[0103] The first film UF1 is, for example, a spin-on glass (SOG) film, a SiC film, a SiON film, a Si-containing antireflection film (SiARC), or an organic film. The second film UF2 is, for example, a spin-on carbon (SOC) film, an amorphous carbon film, or a silicon-containing film. The third film UF3 is, for example, a silicon-containing film. The silicon-containing film is, for example, a silicon oxide film, a silicon nitride film, a silicon oxynitride film, a silicon carbonitride film, a polysilicon film, or a carbon-containing silicon film. The third film UF3 can be composed of multiple laminated silicon-containing films. For example, the third film UF3 can be composed of alternately laminated silicon oxide films and silicon nitride films. In addition, the third film UF3 can also be composed of laminated silicon oxide films and polysilicon films. In addition, the third film UF3 can also be a laminated film containing a silicon nitride film, a silicon oxide film, and a polysilicon film. In addition, the third film UF3 can be composed of laminated silicon oxide films and silicon carbonitride films. In addition, the third film UF3 can also be a laminated film containing a silicon oxide film, a silicon nitride film, and a silicon carbonitride film.

[0104] Part or all of the bottom film UF can be formed in the processing chamber 102 of the heat treatment apparatus 100. In addition, other systems, such as a plasma processing system (refer to Figure 2 and Figure 3 ) or a liquid processing system (refer to Figure 4 ) can also be used for formation.

[0105] (Process ST2: Forming a metal-containing resist film)

[0106] Next, in step ST2, a metal-containing resist film RM is formed on the underlayer film UF of the substrate W. In step ST2, in order to form the metal-containing resist film RM on the underlayer film UF, a metal-containing precursor having a photosensitive group and a polyfunctional compound can be used. The photosensitive group refers to a group that can be detached by exposure due to the photosensitivity of adjacent metal atoms. Examples of the photosensitive group include a hydrogen atom, a hydrocarbon group g1 that can be substituted with a halogen, etc. Examples of the hydrocarbon group g1 that can be substituted include linear or branched alkyl groups such as a methyl group, an ethyl group, a n-propyl group, a n-butyl group, an isopropyl group, a tert-butyl group, and -CH x F y (where x represents an integer from 0 to 2, and y represents an integer from 1 to 3) and other halogen-substituted alkyl groups, etc.

[0107] Figure 8 FIG. is a cross-sectional structure example of the substrate W on which the metal-containing resist film RM is formed in step ST2. As Figure 8 shown, the metal-containing resist film RM is formed on the surface of the underlayer film UF. The metal-containing resist film RM is a film containing a metal. In one embodiment, the metal-containing resist film RM contains at least one metal selected from the group consisting of Sn, Ti, Hf, Zr, and In. In one example, the metal-containing resist film RM may contain Sn.

[0108] In one embodiment, the metal-containing resist film RM contains a compound having a repeating unit represented by the following formula (1) in the molecule:

[0109] -(M-X-A-X)- (1)

[0110] (In formula (1), M represents Sn, Ti, Hf, Zr, or In, X represents a divalent group derived from the terminal functional group of a polyol, a polythiol, a polycarboxylic acid, a polyisocyanate, or a polyisothiocyanate, and A represents a divalent organic group having 2 or more and 10 or less carbon atoms).

[0111] In one example, the divalent group derived from the end of the polyol includes an alkoxy bond. In one example, the divalent group derived from the end of the polythiol includes a sulfur bond. In one example, the divalent group derived from the end of the polycarboxylic acid includes an ester bond. In one example, the divalent group derived from the end of the polyisocyanate includes a urethane bond. In one example, the divalent group derived from the end of the polyisothiocyanate includes a thiocarbamate bond. Examples of the divalent organic group that can provide A in formula (1) include a hydrocarbon group g2 having 2 or more and 10 or less carbon atoms that can be substituted. Examples of the hydrocarbon group g2 that can be substituted include linear, branched, or cyclic divalent hydrocarbon groups. Examples of the linear, branched, or cyclic divalent hydrocarbon groups may include linear, branched, or cyclic alkylene groups or arylene groups. The above linear, branched, or cyclic alkylene groups or arylene groups can each be substituted with at least one hydrogen atom in the molecule by a halogen, etc.

[0112] In one example, the repeating unit represented by formula (1) can be M = Sn, X = -S-, and A = ethylene group. An exemplary process for obtaining a compound having such a repeating unit is as follows Figure 9 shown. In Figure 9 the example of Figure 9 the metal-containing precursor having a photosensitive group is n-butyltri(dimethylamino)tin, and the polyfunctional compound is ethanedithiol. That is, in 2 H 2 the example of

[0113] In one embodiment, step ST2 can be formed by dry film formation. In dry film formation, for example:

[0114] In one embodiment, the metal-containing precursor can contain a compound (α) having an amino group and / or an alkoxy group;

[0115] In one embodiment, the compound (α) can contain a compound (α1), and the compound (α1) contains at least one metal selected from the group consisting of Sn, Ti, Hf, Zr, and In;

[0116] In one embodiment, the compound (α1) can contain Sn;

[0117] In one embodiment, the photosensitive group in the metal-containing precursor can contain at least one group selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, and -CH x F y (where x represents an integer from 0 to 2, and y represents an integer from 1 to 3);

[0118] In one embodiment, the polyfunctional compound can contain at least one compound (β) selected from the group consisting of polyols, polythiols, polycarboxylic acids, polyisocyanates, and polyisothiocyanates;

[0119] In one embodiment, in the step of (b), it is possible to further use at least one selected from the group consisting of H 2 O, H 2 O 2 O 3 O 2 and O

[0120] In dry film formation, the formation of the metal-containing resist film RM in process ST2 can be performed using various methods such as atomic layer deposition (hereinafter referred to as "ALD method") and CVD method. Hereinafter, various methods for forming the metal-containing resist film RM will be described.

[0121] (ALD method)

[0122] In one embodiment, in the ALD method, the metal-containing resist film RM is formed by self-controlled adsorption and reaction of a specified material on the bottom film UF of the substrate W. In one embodiment, the process of (b) can include: (b1) a process of supplying a gas containing a metal-containing precursor to the bottom film to form a metal-containing precursor film; and (b2) a process of supplying a gas containing a polyfunctional compound to the metal-containing precursor film to form a metal-containing resist film from the metal-containing precursor film. In one embodiment, the processes of (b1) and (b2) can be repeated multiple times.

[0123] Figure 10 is a flowchart showing an example of process ST2 using the ALD method. As Figure 10 shown, process ST2 using the ALD method includes: a process ST211 of forming a metal-containing precursor film, a first purge process ST212, a process ST213 of forming a metal film from the metal-containing precursor film, a second purge process ST214, and a determination process ST215. In addition, the first purge process ST212 and the second purge process ST214 may not be performed. In addition, Figure 11 is a diagram schematically showing an example of the phenomenon generated on the surface of the substrate W in process ST21 using the ALD method.

[0124] In process ST211, as Figure 11 shown, a first gas G1 containing a metal-containing precursor is supplied to the surface of the bottom film UF to form a metal-containing precursor film PF. In one embodiment, the metal-containing precursor includes a compound (α) having an amino group and / or an alkoxy group. The amino group is a monovalent group represented by -NR a R b where R a and R bEach independently represents an alkyl group having 1 to 2 carbon atoms. Examples of the amino group include dimethylamino, diethylamino, ethylmethylamino, etc. Examples of the alkoxy group include methoxy, ethoxy, n-propoxy, n-butoxy, isopropoxy, tert-butoxy, etc. In one embodiment, compound (α) can include compound (α1), and compound (α1) includes at least one metal selected from the group consisting of Sn, Ti, Hf, Zr, and In. In one embodiment, compound (α1) can include Sn. In one embodiment, the photosensitive group in the metal-containing precursor can include at least one group selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, and -CH x F y (where x represents an integer from 0 to 2 and y represents an integer from 1 to 3). For example, the metal-containing precursor includes at least one compound selected from the group consisting of an amino tin compound, an amino titanium compound, an amino hafnium compound, an amino zirconium compound, and an amino indium compound. Examples of the amino tin compound can include n-butyltris(dimethylamino)tin, tert-butyltris(dimethylamino)tin, bis(dimethylamino)dimethyltin, bis(dimethyl)dibutyltin, azidotrimethyltin, bis(dimethylamino)dibutyltin, etc. Examples of the alkoxy tin compound can include bis(tert-butoxy)dimethyltin, bis(dimethoxy)dimethyltin. Examples of the amino titanium compound, the amino hafnium compound, and the amino zirconium compound can include compounds represented by the general formula MR x L y (where M is Ti, Hf, or Zr, R is a photosensitive group, L is an amino group or an alkoxy group capable of reacting with a polyfunctional compound, and x and y are such that x≥1 and y = 4 - x). Examples of the amino indium compound can include compounds represented by the general formula InR x L y (where R is a photosensitive group, L is an amino group or an alkoxy group capable of reacting with a polyfunctional compound, and x and y satisfy x≥1 and y = 3 - x). In one embodiment, the photosensitive group in the metal-containing precursor can include at least one group selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, and -CH x F y (where x represents an integer from 0 to 2 and y represents an integer from 1 to 3).

[0125] In step ST211 in one embodiment, the first gas G1 is supplied into the processing chamber 102 via the gas nozzle 141. Then, in the processing chamber 102, the metal-containing precursor of the first gas G1 is adsorbed on the surface of the bottom film UF to form a metal-containing precursor film PF. The metal-containing precursor film PF can include, for example, Sn, Ti, Hf, Zr, In, etc. The metal-containing precursor film PF can be a metal complex. The metal complex can include, for example, amino tin.

[0126] In process ST212, the gas in the processing chamber 102 is discharged from the exhaust port 131 through the exhaust mechanism 132. At this time, an inert gas or the like can be supplied to the substrate W. Thereby, excessive gases such as metal precursor-containing gases are purged. The inert gas is, in one example, a noble gas such as He, Ar, Ne, Kr, Xe or nitrogen gas.

[0127] In process ST213, as Figure 11 shown, a second gas G2 containing a polyfunctional compound is supplied to the surface of the substrate W. The second gas G2 reacts with the metal precursor film PF to form a metal-containing resist film from the metal precursor film PF. The second gas G2 is a gas that reacts with the metal precursor adsorbed on the surface of the bottom film UF. Water and hydrogen peroxide are not included in the polyfunctional compound. In one embodiment, as the polyfunctional compound, a compound having two or more functional groups (a compound having a functional group number of 2 or more) can be used. In one embodiment, the polyfunctional compound can be binary or ternary or more. In one embodiment, the polyfunctional compound may include at least one compound (β) selected from the group consisting of polyols, polythiols, polycarboxylic acids, polyisocyanates and polyisothiocyanates. Examples of polyols may include ethylene glycol, glycerol, etc. Examples of polythiols may include ethanedithiol, toluenedithiol, etc. Examples of polycarboxylic acids may include glutaric acid, adipic acid, terephthalic acid (solution), etc. Examples of polyisocyanates may include toluene diisocyanate, etc. Examples of polyisothiocyanates may include butane diisothiocyanate, phenylenediisothiocyanate, etc. In process ST213 in one embodiment, the second gas G2 is supplied into the processing chamber 102 via the gas nozzle 141. In one embodiment, the second gas G2 may include at least one selected from the group consisting of H 2 O gas, H 2 O 2 、O 3 and O 2 . In one embodiment, at least one selected from the group consisting of H 2 O gas, H 2 O 2 、O 3 and O 2 is supplied into the processing chamber 102 as a gas different from the second gas G2. Then, in the processing chamber 102, the second gas G2 reacts with the metal precursor film PF to form a metal-containing resist film.

[0128] In process ST214, the gas in the processing chamber 102 is discharged from the exhaust port 131 through the exhaust mechanism 132. At this time, an inert gas or the like can be supplied to the substrate W. Thereby, excessive gases such as the second gas G2 are purged.

[0129] In process ST215, it is determined whether a given condition for ending process ST21 is satisfied. The given condition may be that the process from process ST211 to process ST214 is performed a preset number of times for one cycle. This number of times may be 1 time, less than 5 times, more than 5 times, or more than 10 times. In process ST215, when it is determined that the given condition is not satisfied, the process returns to process ST211, and when it is determined that the given condition is satisfied, process ST21 ends. For example, the given condition may also be a condition related to the size of the metal-containing resist film after process ST214. That is, after process ST214, it can be determined whether the size (thickness of the resist film) of the metal-containing resist film has reached a given value or range, and the cycle of processes ST211 to ST214 is repeated until the given value or range is reached. The size of the metal-containing resist film can be measured by an optical measuring device. Thus, a metal-containing resist film is formed on the bottom film UF.

[0130] (CVD method)

[0131] In one embodiment, the CVD method forms a metal-containing resist film through a mixed gas GM containing a metal-containing precursor and a polyfunctional compound. The metal-containing precursor may include a known metal-containing precursor usable in the CVD method (in the case of containing Si, a silicon-containing compound, etc.), or may be a metal-containing precursor described in the ALD method. The polyfunctional compound may be a polyfunctional compound described in the ALD method. The mixed gas GM may include at least one selected from the group consisting of H 2 O, H 2 O 2 、O 3 and O 2 composed of. In one embodiment, the mixed gas GM is supplied into the processing chamber 102 via the gas nozzle 141. The mixed gas GM undergoes a chemical reaction on the substrate W, thereby forming a metal-containing resist film on the bottom film UF.

[0132] In process ST2, the temperature and pressure of the substrate support portion 121 can be appropriately set. The temperature adjustment of the substrate support portion 121 can be performed by controlling the output of one or more of each heater. The temperature of the substrate support portion 121 can be, for example, 25 to 350 °C, and in one example, 50 to 200 °C. The pressure in the processing chamber 102 can be, for example, 500 Torr or less.

[0133] In one embodiment, the process ST2 may include a process of heating and baking the metal-containing resist film. The baking may be performed in an atmospheric environment or in an inert gas environment. The baking may be carried out by heating the substrate W to a temperature of 50°C or higher and 350°C or lower, 50°C or higher and 200°C or lower, or 80°C or higher and 150°C or lower. In one embodiment, each heater of the heat treatment apparatus 100 may function as a heating unit for performing the baking. In one embodiment, the baking may be performed using a heat treatment system other than the heat treatment apparatus 100.

[0134] In one embodiment, the processing method may be performed by using a drying process of a plasma processing system (refer to Figure 2 and Figure 3 ). For example, the substrate W may be provided on the substrate support portion 11 in the processing chamber 10 of the plasma processing apparatus 1 (process ST1), and a metal-containing resist film RM may be formed by supplying a processing gas into the processing chamber 10 by the gas supply unit 20 (process ST2).

[0135] In the case of using a plasma processing system, in process ST2, the above-described ALD method or CVD method may be used. The composition (type, flow rate, and flow rate ratio) of the processing gas (first gas G1, second gas G2, mixed gas GM, etc.) in process ST2 and the temperature of the substrate support portion 11 may be the same as those in the case of using a heat treatment system. The temperature of the substrate support portion 11 may be adjusted by controlling the temperature control module or the pressure of the heat transfer gas (e.g., He) between the electrostatic chuck 1111 and the back surface of the substrate W. In processes ST21 and ST22, plasma may or may not be generated from the processing gas. Similar to the case of using a heat treatment system (refer to Figure 1 ), process ST21 and / or process ST22 may include a process of heating the substrate W and performing a baking process. The baking process may be performed using a heat treatment system, for example.

[0136] In one embodiment, the processing method may be performed by using a wet process (wet film formation) of a liquid processing system (refer to Figure 4 ). That is, the substrate W may be provided on the rotating chuck 311 in the processing chamber 310 of the liquid processing apparatus 300 (process ST1), and a film-forming solution (resist precursor liquid) may be coated on the substrate W by the processing liquid supply nozzle 331 to form a metal-containing resist film RM (process ST2). In one embodiment, when process ST2 is implemented by wet film formation, for example:

[0137] In one embodiment, the process of (b) includes a process of coating a solution containing a metal-containing precursor and a polyfunctional compound on the bottom film and a process of heating the coated solution;

[0138] In one embodiment, the metal-containing precursor includes a metal complex, and the metal complex contains at least one metal selected from the group consisting of Sn, Ti, Hf, Zr, and In;

[0139] In one embodiment, the polyfunctional compound contains at least one compound (β) selected from the group consisting of polyols, polythiols, polycarboxylic acids, polyisocyanates, and polyisothiocyanates.

[0140] In the case of using a liquid processing system, in step ST2, the film-forming solution (resist precursor liquid) may contain a metal-containing precursor. In one embodiment, the metal-containing precursor contains a compound (α) having an amino group. In one embodiment, the compound (α) may contain a compound (α1), and the compound (α1) contains at least one metal selected from the group consisting of Sn, Ti, Hf, Zr, and In. In one embodiment, the compound (α1) may contain Sn. In one embodiment, the photosensitive group in the metal-containing precursor may contain at least one group selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, and -CH x F y (where x represents an integer from 0 to 2 and y represents an integer from 1 to 3). For example, the metal-containing precursor contains at least one compound selected from the group consisting of amino tin compounds, amino titanium compounds, amino hafnium compounds, amino zirconium compounds, and amino indium compounds. Examples of amino tin compounds may include n-butyltris(dimethylamino)tin, tert-butyltris(dimethylamino)tin, bis(dimethylamino)dimethyltin, bis(dimethyl)dibutyltin, azidotrimethyltin, bis(dimethylamino)dibutyltin, etc. Examples of alkoxy tin compounds may include bis(tert-butoxy)dimethyltin, bis(dimethoxy)dimethyltin. Examples of amino titanium compounds, amino hafnium compounds, and amino zirconium compounds may include compounds represented by the general composition formula of MR x L y (where M is Ti, Hf, or Zr, R is a photosensitive group, L is an amino group or an alkoxy group that can react with the polyfunctional compound, and x and y are such that x≥1 and y = 4 - x). Examples of amino indium compounds may include compounds represented by the general composition formula of InR x L y (where R is a photosensitive group, L is an amino group or an alkoxy group that can react with the polyfunctional compound, and x and y satisfy x≥1 and y = 3 - x).

[0141] In the case of using a liquid processing system, in step ST2, the film-forming solution (resist precursor liquid) may contain a polyfunctional compound. In one embodiment, the polyfunctional compound may contain at least one compound (β) selected from the group consisting of polyols, polythiols, polycarboxylic acids, polyisocyanates, and polyisothiocyanates. Examples of polyols may include ethylene glycol, glycerol, etc. Examples of polythiols may include ethylene dithiol, toluene dithiol, etc. Examples of polycarboxylic acids may include glutaric acid, adipic acid, terephthalic acid (solution), etc. Examples of polyisocyanates may include toluene diisocyanate, etc. Examples of polyisothiocyanates may include butyl diisothiocyanate, phenylenediisothiocyanate, etc. The second gas G2 may include at least one selected from the group consisting of H 2 O gas, H 2 O 2 、O 3 and O 2 .

[0142] In the case of using a liquid processing system, step ST2 may include a step of heating and baking the substrate W after coating the solution on the substrate W. In one embodiment, for example, a heat treatment system (refer to Figure 1 ) can be used to perform the baking. The baking can be performed in an atmospheric environment or in an inert gas environment. The baking can be performed by heating the substrate W to a temperature of 50°C or higher and 350°C or lower, 50°C or higher and 200°C or lower, or 80°C or higher and 150°C or lower.

[0143] In one embodiment, the formation of the metal-containing resist film RM in this processing method (step ST2) can be carried out in both a dry process using a heat treatment system (refer to Figure 1 ) or a plasma processing system (refer to Figure 2 and Figure 3 ) and a wet process using a liquid processing system (refer to Figure 4 ).

[0144] In one embodiment, through the reaction of the metal-containing precursors and the polyfunctional compound in step ST2, the metal-containing precursors are bonded to each other via the structure derived from the polyfunctional compound, thereby reducing the composition ratio and film density of the metal in the metal-containing resist film. By reducing the composition ratio and film density of the metal, in the subsequent possible development, not only substances with high reactivity (such as highly corrosive substances like hydrogen chloride, boron chloride, hydrogen bromide, etc.) are used, but even organic acids described later tend to react sufficiently to form a metal-containing resist film. In one embodiment, by bonding the metal-containing precursors to each other via the structure derived from the polyfunctional compound, a chemical structure with a relatively weak binding force of -Sn-X-A-X-Sn- (where X and A are the same as defined in formula (1)) is obtained compared to the conventional bond such as -Sn-O-Sn-, and at the same time the film density is reduced, and in the subsequent possible development, the reactivity tends to increase. In one embodiment, during the reaction of the metal-containing precursor and the polyfunctional compound in step ST2, the type of the polyfunctional compound used over time can be changed. As a specific example thereof, in the initial stage of the reaction (from the start of the reaction to the first elapsed time), a polyfunctional compound having a first carbon number is used. Then, in the middle stage of the reaction (from the first elapsed time to the second elapsed time), a polyfunctional compound having a second carbon number larger than the first carbon number is used. Further, in the final stage of the reaction (from the second elapsed time to the end of the reaction), a polyfunctional compound having a third carbon number larger than the second carbon number is used. In such an example, a metal-containing resist film having a composition and / or density gradient in the film formation direction (a metal-containing resist film with a high density (high composition ratio of metal) on the lower layer side and a low density (low composition ratio of metal) on the upper layer side) can be obtained. From the same viewpoint, as another specific example, in the initial stage of the reaction, a polyfunctional compound having a first number of functional groups is used. Then, in the middle stage of the reaction, a polyfunctional compound having a second number of functional groups smaller than the first number of functional groups is used. Further, in the final stage of the reaction, a polyfunctional compound having a third number of functional groups smaller than the second number of functional groups is used. In such an example, a metal-containing resist film having a density gradient in the film formation direction (a metal-containing resist film with a high density (high composition ratio of metal) on the lower layer side and a low density (low composition ratio of metal) on the upper layer side) can also be obtained.

[0145] Whether this treatment method is implemented by dry film formation or by wet film formation, in one embodiment, this treatment method further includes: (c) after the step of (b), exposing the substrate to form an exposed first region and an unexposed second region on the metal-containing resist film; and (d) developing the substrate to selectively remove the second region from the metal-containing resist film.

[0146] In one embodiment, in the process of (d), the second region can be removed by a developing gas or a developer. In one embodiment, the developing gas or the developer may contain an organic acid. In one embodiment, the organic acid can include at least one selected from the group consisting of alcohols, thiols, carboxylic acids, sulfonic acids, β-dicarbonyl compounds, alkyl carbonates, and azoles. When these organic acids are used, the contrast of development tends to increase. Examples of alcohols may include perfluorotert-butanol ((CF 3 )) 3 C-OH), trifluoroethanol, and the like. Examples of thiols may include methanethiol, allyl mercaptan, trifluoroethyl mercaptan, and the like. Examples of carboxylic acids may include formic acid (HCOOH), acetic acid (CH 3 COOH), trichloroacetic acid (CCl 3 COOH), monofluoroacetic acid (CFH 2 COOH), difluoroacetic acid (CF 2 FCOOH), trifluoroacetic acid (CF 3 COOH), chlorodifluoroacetic acid (CClF 2 COOH), sulfur-containing acetic acid, thioacetic acid (CH 3 COSH), mercaptoacetic acid (HSCH 2 COOH), trifluoroacetic anhydride ((CF 3 CO) 2 O), acetic anhydride ((CH 3 CO) 2 O), and the like. Examples of sulfonic acids may include methanesulfonic acid, fluorosulfonic acid, 10-camphorsulfonic acid, and the like. Examples of β-dicarbonyl compounds may include acetylacetone (CH 3 C(O)CH 2 C(O)CH 3 ), trichloroacetylacetone (CCl 3 C(O)CH 2 C(O)CH 3 ), hexachloroacetylacetone (CCl 3 C(O)CH 2 C(O)CCl 3 ), trifluoroacetylacetone (CF 3 C(O)CH 2 C(O)CH 3 ), hexafluoroacetylacetone (HFAc, CF 3 C(O)CH 2 C(O)CF 3) etc. Examples of the alkyl carbonate may include dimethyl carbonate etc. Examples of the azole may include 1,2,3-triazole etc. The developing gas or the developing liquid may contain an inorganic acid. In one embodiment, the developing gas may include a halogen-containing gas. The halogen-containing gas may be a gas containing a halogen-containing inorganic acid or a gas containing Br or Cl. The gas containing a halogen-containing inorganic acid is, in one example, at least one selected from the group consisting of HBr gas, BCl 3 gas, HCl gas, HF gas, and HI gas. In one embodiment, the processing gas is a mixed gas of a carboxylic acid and a hydrogen halide, or a mixed gas of acetic acid and formic acid. In one embodiment, the developing liquid may be a liquid containing the above-mentioned halogen-containing inorganic acid.

[0147] In one embodiment, in the step (d), the second region may be removed by a developing gas or a developing liquid containing a weak acid. In one embodiment, the weak acid may contain an organic acid having an acid dissociation constant (pKa) of less than 16. For example, an organic acid having an acid dissociation constant (pKa) of less than 16 may be selected from the above-mentioned organic acids for use. In one embodiment, the weak acid may contain an organic acid having an acid dissociation constant (pKa) of 0 or more and less than 16. For example, an organic acid having an acid dissociation constant (pKa) of 0 or more and less than 16 may be selected from the above-mentioned organic acids for use.

[0148] (Composition for forming a metal-containing resist)

[0149] In one embodiment, in the present processing method, a composition for forming a metal-containing resist may be used, which contains: a metal-containing precursor having a photosensitive group and a polyfunctional compound, and the metal-containing precursor contains a compound having a photosensitive group, an amino group, and / or an alkoxy group. The metal-containing precursor, the polyfunctional compound, etc. in the composition for forming a metal-containing resist may be the same as those described in step ST2. In one embodiment, the composition for forming a metal-containing resist may be a gas mixture containing a gas of a metal-containing precursor and a gas of a polyfunctional compound. In one embodiment, the composition for forming a metal-containing resist may be a liquid mixture containing a liquid of a metal-containing precursor and a liquid of a polyfunctional compound.

[0150] (Metal-containing resist)

[0151] In one embodiment, the metal-containing resist film obtained by the present processing method may contain the following metal-containing resist. That is, in one embodiment, the metal-containing resist contains a compound having a repeating unit represented by the following formula (1) in the molecule.

[0152] -(M-X-A-X)-(1)

[0153] (In formula (1), M represents Sn, Ti, Hf, Zr, or In, X represents a divalent group derived from a terminal functional group of a polyol, polythiol, polycarboxylic acid, polyisocyanate, or polyisothiocyanate, and A represents a divalent organic group having 2 or more and 10 or less carbon atoms).

[0154] The polyols, polythiols, polycarboxylic acids, polyisocyanates, and polyisothiocyanates that can provide X in formula (1) can be the same as those described in process ST2. In one example, the divalent group derived from the polyol terminal includes an alkoxy bond. In one example, the divalent group derived from the polythiol terminal includes a sulfur bond. In one example, the divalent group derived from the polycarboxylic acid terminal includes an ester bond. In one example, the divalent group derived from the polyisocyanate terminal includes a urethane bond. In one example, the divalent group derived from the polyisothiocyanate terminal includes a thiocarbamate bond.

[0155] Examples of the divalent organic group that can provide A in formula (1) include a substitutable hydrocarbon group g2 having 2 or more and 10 or less carbon atoms. Examples of the substitutable hydrocarbon group g2 include linear, branched, or cyclic divalent hydrocarbon groups. Examples of the linear, branched, or cyclic divalent hydrocarbon groups can include linear, branched, or cyclic alkylene or arylene groups. The above linear, branched, or cyclic alkylene or arylene groups can each substitute at least one hydrogen atom in the molecule with a halogen or the like.

[0156] <Configuration example of substrate processing system>

[0157] Figure 12 It 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.

[0158] The first carrier station CS1 transfers the first carrier C1 in or out between the first carrier station CS1 and an external system of the substrate processing system SS. The first carrier station CS1 has a stage including a plurality of first mounting plates ST1. The first carrier C1 in a state of accommodating a plurality of substrates W or in an idle state is mounted on each first mounting plate ST1. 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).

[0159] In addition, the first carrier station CS1 transports the substrate W between the first carrier C1 and the first processing station PS1. The first carrier station CS1 further includes a first transfer device HD1. The first transfer device HD1 is arranged between the placement table and the first processing station PS1 in the first carrier station CS1. The first transfer device HD1 transports and transfers the substrate W between the first carrier C1 on each first placement plate ST1 and the second transfer device HD2 of the first processing station PS1. The substrate processing system SS may further include a load lock module. The load lock module may be arranged between the first carrier station CS1 and the first processing station PS1. The load lock module can 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 0.1 Pa - 100 Pa. The inside 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 as atmospheric pressure to the second transfer device HD2 as vacuum, and also transfer the substrate W from the second transfer device HD2 as vacuum to the first transfer device HD1 as atmospheric pressure.

[0160] 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 (collectively referred to as "the first substrate processing module PMa" hereinafter). In addition, the first processing station PS1 has a second transfer device HD2 for transporting the substrate W. The second transfer device HD2 transports and transfers the substrate W between two specified first substrate processing modules PMa, and between the first processing station PS1 and the first carrier station CS1 or the first interface station IS1.

[0161] In the pre-processing module PM1, pre-processing is performed on the substrate W. 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 precisely adjusting the temperature of the substrate W, and a bottom film forming unit for forming part or all of the bottom film on the substrate. In one embodiment, the pre-processing module PM1 includes a surface modification processing unit for performing surface modification processing on the substrate W. Each processing unit of the pre-processing module PM1 may include a heat treatment device 100 (refer to Figure 1 ), a plasma processing device 1 (refer to Figure 2 and 3 ) and / or a liquid processing device 300 (refer to Figure 4 ).

[0162] 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 a resist film on the substrate W using a dry process such as chemical vapor deposition. In one example, the dry coating unit includes a CVD apparatus or an ALD apparatus that chemically vapor-deposits a resist film on the substrate W disposed in a chamber, or a PVD apparatus that physically vapor-deposits a resist film. The dry coating unit may be a heat treatment apparatus 100 (refer to Figure 1 ) or a plasma processing apparatus 1 (refer to Figure 2 and 3 ).

[0163] 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 liquid deposition. In one example, the wet coating unit may be a liquid processing apparatus 300 (refer to Figure 4 ).

[0164] In one embodiment, an example of the resist film forming module PM2 includes both a wet coating unit and a dry coating unit.

[0165] In the first heat treatment module PM3, heat treatment is performed on the substrate W. In one embodiment, the first heat treatment module PM3 includes any one or more of a post apply bake (PAB) unit that heat-treats the substrate W on which a resist film is formed, a temperature adjustment unit that adjusts the temperature of the substrate W, and a high-precision temperature adjustment unit that highly precisely adjusts the temperature of the substrate W. Each of these units may have one or more heat treatment apparatuses. In one example, a plurality of heat treatment apparatuses may be stacked. The heat treatment apparatus may be, for example, a heat treatment apparatus 100 (refer to Figure 1 ). Each heat treatment may be performed using a prescribed gas at a prescribed temperature.

[0166] The first interface station IS1 includes a third transfer device HD3. The third transfer device HD3 transfers and exchanges the substrate W between the first processing station PS1 and the exposure apparatus EX. The third transfer device HD3 may have a frame that houses the substrate W and is configured to be able to control the temperature, humidity, pressure, etc. inside the frame.

[0167] The exposure apparatus EX exposes the resist film on the substrate W using an exposure mask (photomask). The exposure apparatus EX may be, for example, an EUV exposure apparatus having a light source that generates EUV light.

[0168] The second interface station IS2 has a fourth transfer device HD4. The fourth transfer device HD4 transfers and exchanges the substrate W between the exposure device EX and the second processing station PS2. The fourth transfer device HD4 may have a frame for accommodating the substrate W and is configured to be able to control the temperature, humidity, pressure, etc. inside the frame.

[0169] The second processing station PS2 performs various processes on the substrate W. In one embodiment, the second processing station PS2 includes a second heat treatment module PM4, a measurement module PM5, a development module PM6, and a third heat treatment module PM7 (collectively referred to as the "second substrate processing module PMb" hereinafter). In addition, the second processing station PS2 has a fifth transfer device HD5 for transferring the substrate W. The fifth transfer device HD5 transfers and exchanges 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.

[0170] In the second heat treatment module PM4, heat treatment is performed on the substrate W. In one embodiment, the heat treatment module PM4 includes any one or more of a post-exposure bake (PEB) unit for heating the exposed substrate W, a temperature adjustment unit for adjusting the temperature of the substrate W, and a high-precision temperature control unit for precisely adjusting the temperature of the substrate W. Each of these units may have one or more heat treatment devices. In one example, multiple heat treatment devices may be stacked. The heat treatment device may be, for example, the heat treatment device 100 (refer to Figure 1 ). Each heat treatment can be performed using a specified gas at a specified temperature.

[0171] In the measurement module PM5, various measurements are performed on the substrate W. In one embodiment, the measurement module PM5 includes a stage for placing the substrate W, an imaging device, an illumination device, and an imaging unit including various sensors (temperature sensors, reflectivity measurement sensors, etc.). The imaging device may be, for example, a CCD camera for photographing the appearance of the substrate W. Alternatively, the imaging device may also be a hyperspectral camera that splits light by each wavelength and takes a photograph. The hyperspectral camera can measure any one or more of the pattern shape, size, film thickness, composition, and film density of the resist film.

[0172] In the development module PM6, a development process is performed on the substrate W. In one embodiment, the development module PM6 includes a dry development unit for performing dry development on the substrate W. The dry development unit may be, for example, the heat treatment device 100 (refer to Figure 1 ) or the plasma processing device 1 (refer to Figure 2 and Figure 3)。In one embodiment, the development module PM6 includes a wet development unit that performs wet development on the substrate W. The wet development unit can be, for example, the liquid processing apparatus 300( Figure 4 )。In one embodiment, the development module PM6 includes both a dry development unit and a wet development unit.

[0173] In the third heat treatment module PM7, heat treatment is performed on the substrate W. In one embodiment, the third heat treatment module PM7 includes any one or more of a post bake (PB) unit that performs heat treatment on the developed substrate W, a temperature adjustment unit that adjusts the temperature of the substrate W, and a high-precision temperature adjustment unit that highly precisely adjusts the temperature of the substrate W. Each of these units can have one or more heat treatment apparatuses. In one example, a plurality of heat treatment apparatuses can be stacked. The heat treatment apparatus can be, for example, the heat treatment apparatus 100 (refer to Figure 1 )。Each heat treatment can be performed using a prescribed gas at a prescribed temperature.

[0174] The second carrier station CS2 carries in and 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 can be the same as those of the above-described first carrier station CS1.

[0175] The control unit CT controls each structure of the substrate processing system SS and performs a given process on the substrate W. The control unit CT stores a process in which a process sequence, process conditions, transfer conditions, etc. are set, and in accordance with this process, controls each structure of the substrate processing system SS and performs a given process on the substrate W. The control unit CT can have a part or all of the functions of each control unit ( Figures 1 to 4 the control unit 200, the control unit 2, and the control unit 400 shown).

[0176] <An example of a substrate processing method>

[0177] Figure 13 is a flowchart showing a substrate processing method (hereinafter also referred to as "method MT") according to an exemplary embodiment. As Figure 13As shown, method MT includes: a process ST100 of performing pre-treatment on a substrate, a process ST200 of forming a resist film on the substrate, a process ST300 of performing a heat treatment (pre-baking: PAB) on the substrate on which the resist film is formed, a process ST400 of performing EUV exposure on the substrate, a process ST500 of performing a heat treatment (post-exposure baking: PEB) on the exposed substrate, a process ST600 of measuring the substrate, a process ST700 of developing the resist film of the substrate, a process ST800 of performing a heat treatment (post-baking: PB) on the developed substrate, and a process ST900 of etching the substrate. Method MT may not include one or more of the above processes. For example, method MT may not include process ST600, and process ST700 may be executed after process ST500.

[0178] Method MT may use Figure 12 the substrate processing system SS shown to execute. Hereinafter, taking the case where the control unit CT of the substrate processing system SS controls each part of the substrate processing system SS and executes method MT on the substrate W as an example for explanation.

[0179] (Process ST100: Pre-treatment)

[0180] First, the first carrier C1 accommodating a plurality of substrates W is carried into the first carrier station CS1 of the substrate processing system SS. The first carrier C1 is placed on the first mounting plate ST1. Then, each substrate W in the first carrier C1 is sequentially taken out by the first transfer device HD1 and handed over to the second transfer device HD2 of the first processing station PS1. The substrate W is transferred to the pre-treatment module PM1 by the second transfer device HD2. The substrate W is pre-treated by the pre-treatment module PM1. The pre-treatment may include, for example, one or more of temperature adjustment of the substrate W, formation of a part or all of the bottom film of the substrate W, heat treatment of the substrate W, and high-precision temperature adjustment of the substrate W. As another example, the pre-treatment may include surface modification treatment of the substrate W.

[0181] (Process ST200: Resist Film Formation)

[0182] Next, the substrate W is transported to the resist film forming module PM2 by the second transfer 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 such as a liquid phase deposition method. For example, a resist film is formed by spin-coating a resist film on the substrate W using the 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 vapor-depositing a resist film on the substrate W using the dry coating unit of the resist film forming module PM2. The formation of the resist film in the process ST200 can be performed using this processing method (refer to Figure 5 ). That is, a metal-containing resist film RM can be formed on the substrate W.

[0183] In addition, the formation of the resist film on the substrate W can also be performed using both a dry process and a wet process. For example, after a first resist film is formed on the substrate W by a dry process, a second resist film can be formed on the first resist film by a wet process. At this time, the film thickness, material, and / or composition of the first resist film and the second resist film can be the same or different.

[0184] (Process ST300: PAB)

[0185] Next, the substrate W is transported to the first heat treatment module PM3 by the second transfer device HD2. The substrate W is subjected to a heat treatment (pre-baking: PAB) by the first heat treatment module PM3. The pre-baking can be performed in an atmospheric environment or in an inert gas environment. In addition, the pre-baking can be performed by heating the substrate W to 50 °C or higher or 80 °C or higher. The heating temperature of the substrate W can be 250 °C or lower, 200 °C or lower, or 150 °C or lower. In one example, the heating temperature of the substrate can be 50 °C or higher and 250 °C or lower. When the resist film is formed by a dry process in the process ST200, in one embodiment, the pre-baking can be continuously performed in the dry coating unit that executes the process ST200. In one embodiment, after the pre-baking, a process of removing the resist film at the end of the substrate W (Edge Bead Removal: EBR) can be performed.

[0186] (Process ST400: EUV exposure)

[0187] Next, the substrate W is transferred from the second transfer device HD2 to the third transfer device HD3 of the first interface station IS1. Then, the substrate W is transferred to the exposure apparatus EX by the third transfer device HD3. The substrate W is EUV-exposed in the exposure apparatus EX via an exposure mask (photomask). EUV has a wavelength in the range of, for example, 10 to 20 nm. EUV can have a wavelength in the range of 11 to 14 nm and, in one example, has a wavelength of 13.5 nm. Thus, on the substrate W, a first region that has been EUV-exposed and a second region that has not been EUV-exposed are formed corresponding to the pattern of the exposure mask (photomask). The film thickness of the first region is smaller than that of the second region.

[0188] (Process ST500: PEB)

[0189] Next, the substrate W is transferred from the fourth transfer device HD4 of the second interface station IS2 to the fifth transfer device HD5 of the second processing station PS2. Then, the substrate W is transferred to the second heat treatment module PM4 by the fifth transfer device HD5. Then, a heat treatment (post-exposure bake: PEB) is performed on the substrate W in the second heat treatment module PM4. The post-exposure bake can be performed in an atmospheric environment. In addition, the post-exposure bake can be performed by heating the substrate W to 180 °C or higher and 250 °C or lower.

[0190] (Process ST600: Measurement)

[0191] Next, the substrate W is transferred to the measurement module PM5 by the fifth transfer device HD5. The substrate W is measured by the measurement module PM5. The measurement can be an optical measurement or other measurements. In one embodiment, the measurement by the measurement module PM5 includes measuring the appearance and / or dimensions of the substrate W using a CCD camera. In one embodiment, the measurement by the measurement module PM5 includes measuring any one or more of the pattern shape, dimensions, film thickness, composition, and film density of the resist film (hereinafter also referred to as "pattern shape, etc.") using a hyperspectral camera.

[0192] In one embodiment, the control unit CT determines whether there is an exposure abnormality of the substrate W based on the measured appearance, dimensions, and / or pattern shape, etc. of the substrate W. In one embodiment, when it is determined in the control unit CT that there is an exposure abnormality, development in process ST700 may not be performed, and the substrate W may be reprocessed or discarded. The reprocessing of the substrate W can be performed by removing the resist on the substrate W and returning to process ST200 to form a resist film again. Reprocessing after development sometimes causes damage to the substrate W, but by performing reprocessing before development, damage to the substrate W can be avoided or suppressed.

[0193] (Process ST700: Development)

[0194] Next, the substrate W is transferred to the development module PM6 by the fifth transfer device HD5. In the development module PM6, the resist film on the substrate W is developed. The first region exposed to EUV or the second region not exposed to EUV is selectively removed by development. The development process can be carried out by dry development or by wet development. The development process can also be carried out by combining dry development and wet development. After the development process or during the development process, desorption treatment can be performed more than once. The desorption treatment includes removing scum or smoothing the surface from the surface of the resist film by an inert gas such as helium or a plasma of the inert gas. The development process can also be carried out by heating the substrate W to a temperature above 100 °C and below 350 °C. The dry development process can also be carried out by setting the pressure to 10 Torr or less. The development process can be carried out for 0.5 minutes or more and 2 hours or less. As described above, in one embodiment, this processing method can also be implemented as part of a development method. That is, in one embodiment, the development method includes: (a) a step of providing a substrate having an underlayer film and a metal-containing resist on the underlayer film; (b) a step of exposing the metal-containing resist via an exposure mask to form an exposed first region and an unexposed second region in the metal-containing resist; (c) a step of selectively removing one of the first region and the second region, and the metal-containing resist in (a) contains a compound having a repeating unit represented by the following formula (1) in the molecule.

[0195] (Process ST800: PB)

[0196] Next, the substrate W is transferred to the third heat treatment module PM7 by the fifth transfer device HD5, and a heat treatment (post-baking) is performed. The post-baking can be carried out in an atmospheric environment or in an atmosphere containing N 2 or O 2It is carried out in a reduced-pressure environment. Additionally, the post-baking can be performed by heating the substrate W to a temperature above 150°C and below 250°C. The post-baking can be carried out by the second heat treatment module PM4 instead of the third heat treatment module PM7. In one embodiment, after the post-baking, the substrate W can be optically measured by the measurement module PM5. The involved measurement can be performed in addition to the measurement in process ST600 or can replace the measurement in process ST600. In one embodiment, the control unit CT determines whether there are abnormalities such as defects, scratches, and foreign object attachments in the developed pattern of the substrate W based on the measured appearance, dimensions, and / or pattern shape, etc. of the substrate W. In one embodiment, when it is determined in the control unit CT that there is an abnormality, the substrate W can be reprocessed or discarded without performing the etching based on process ST900. In one embodiment, when it is determined in the control unit CT that there is an abnormality, a dry coating unit (such as a CVD device, an ALD device, etc.) can be used to adjust the opening size of the resist film of the substrate W.

[0197] (Process ST900: Etching)

[0198] After performing process ST800, the substrate W is transferred by the fifth transfer device HD5 to the sixth transfer device HD6 of the second carrier station CS2 and is transferred by the sixth transfer device HD6 to the second carrier C2 of the second stage ST2. Then, the second carrier C2 is transferred to a plasma processing system (not shown). The plasma processing system can 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. Additionally, in process ST700, when using a plasma processing device to develop the resist film, the etching can be continuously performed in the plasma processing chamber of the plasma processing device. Additionally, when the second processing station PS2 has a plasma processing module in addition to the developing module PM6, the etching can also be performed in the plasma processing module. The above-described desorption treatment can be performed one or more times before or during the etching. As described above, in one embodiment, this processing method can also be implemented as part of an etching method. That is, in one embodiment, it includes: (a) a step of providing a substrate having a bottom film and a metal-containing resist on the bottom film, wherein the metal-containing resist has at least one opening; (b) a step of etching the bottom film through the opening, and the metal-containing resist contains a compound having a repeating unit represented by the above formula (1) in the molecule.

[0199] Embodiments of the present disclosure also include the following aspects.

[0200] (Supplementary Note 1)

[0201] A substrate processing method having:

[0202] (a) a step of providing a substrate having a bottom film; and

[0203] (b) a step of forming a metal-containing resist film on the bottom film using a metal-containing precursor having a photosensitive group and a polyfunctional compound.

[0204] (Supplementary Note 2)

[0205] The substrate processing method according to Supplementary Note 1, wherein

[0206] the metal-containing precursor contains a compound (α) having an amino group and / or an alkoxy group.

[0207] (Supplementary Note 3)

[0208] The substrate processing method according to Supplementary Note 2, wherein

[0209] the compound (α) contains a compound (α1), and the compound (α1) contains at least one metal selected from the group consisting of Sn, Ti, Hf, Zr, and In.

[0210] (Supplementary Note 4)

[0211] The substrate processing method according to Supplementary Note 3, wherein

[0212] the compound (α1) contains Sn.

[0213] (Supplementary Note 5)

[0214] The substrate processing method according to any one of Supplementary Notes 1 to 4, wherein

[0215] the photosensitive group contains at least one group selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, and -CH x F y (where x represents an integer from 0 to 2 and y represents an integer from 1 to 3).

[0216] (Supplementary Note 6)

[0217] The substrate processing method according to any one of Supplementary Notes 1 to 5, wherein

[0218] the polyfunctional compound contains at least one compound (β) selected from the group consisting of polyols, polythiols, polycarboxylic acids, polyisocyanates, and polyisothiocyanates.

[0219] (Supplementary Note 7)

[0220] The substrate processing method according to any one of Supplementary Notes 1 to 6, wherein

[0221] In the step (b), at least one selected from the group consisting of H 2 O, H 2 O 2 , O 3 and O 2 is further used.

[0222] (Supplementary Note 8)

[0223] The substrate processing method according to any one of Supplementary Notes 1 to 7, wherein

[0224] the step (b) includes:

[0225] (b1) A step of supplying a gas containing the metal precursor onto the bottom film to form a metal precursor film; and

[0226] (b2) A step of supplying a gas containing the polyfunctional compound onto the metal precursor film to form the metal-containing resist film from the metal precursor film.

[0227] (Supplementary Note 9)

[0228] The substrate processing method according to Supplementary Note 8, wherein

[0229] the steps (b1) and (b2) are repeated multiple times.

[0230] (Supplementary Note 10)

[0231] The substrate processing method according to any one of Supplementary Notes 1 to 9, wherein

[0232] the step (b) includes using a mixed gas containing the metal precursor and the polyfunctional compound to form the metal-containing resist film.

[0233] (Supplementary Note 11)

[0234] The substrate processing method according to any one of Supplementary Notes 1 to 10, wherein

[0235] the metal precursor contains a metal complex, and the metal complex contains at least one metal selected from the group consisting of Sn, Ti, Hf, Zr, and In.

[0236] (Supplementary Note 12)

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

[0238] the polyfunctional compound contains at least one compound (β) selected from the group consisting of polyols, polythiols, polycarboxylic acids, polyisocyanates, and polyisothiocyanates.

[0239] (Supplementary Note 13)

[0240] The substrate processing method according to any one of Supplementary Notes 1 to 12, wherein,

[0241] The step (b) includes:

[0242] A step of coating a solution containing the metal precursor and the polyfunctional compound on the bottom film; and

[0243] A step of heating the coated solution to form a metal-containing resist film.

[0244] (Supplementary Note 14)

[0245] The substrate processing method according to any one of Supplementary Notes 1 to 13, wherein,

[0246] The substrate processing method further includes:

[0247] (c) After the step (b), exposing the substrate, and forming a first exposed region and a second unexposed region in the metal-containing resist film; and

[0248] (d) Developing the substrate, and selectively removing the second region from the metal-containing resist film.

[0249] (Supplementary Note 15)

[0250] The substrate processing method according to Supplementary Note 14, wherein,

[0251] In the step (d), the second region is removed by a developing gas or a developing solution containing a weak acid.

[0252] (Supplementary Note 16)

[0253] The substrate processing method according to Supplementary Note 15, wherein,

[0254] The weak acid contains an organic acid with an acid dissociation constant (pKa) less than 16.

[0255] (Supplementary Note 17)

[0256] The substrate processing method according to Supplementary Note 16, wherein,

[0257] The organic acid contains at least one selected from the group consisting of alcohols, thiols, carboxylic acids, sulfonic acids, β-dicarbonyl compounds, alkyl carbonates, and azoles.

[0258] (Supplementary Note 18)

[0259] A composition for forming a metal-containing resist, comprising:

[0260] A metal-containing precursor having a photosensitive group; and

[0261] A polyfunctional compound,

[0262] The metal-containing precursor includes a compound having a photosensitive group, an amino group, and / or an alkoxy group.

[0263] (Supplementary Note 19)

[0264] A metal-containing resist comprising a compound having a repeating unit represented by the following formula (1) in the molecule:

[0265] -(M-X-A-X)-(1)

[0266] (In the above formula (1), M represents Sn, Ti, Hf, Zr, or In, X represents a divalent group derived from a terminal functional group of a polyol, a polythiol, a polycarboxylic acid, a polyisocyanate, or a polyisothiocyanate, and A represents a divalent organic group having 2 or more and 10 or less carbon atoms).

[0267] (Supplementary Note 20)

[0268] A substrate processing system, which is a substrate processing system having one or more substrate processing devices and a control unit,

[0269] The control unit is configured to perform the following control on the one or more substrate processing devices:

[0270] (a) Control for providing a substrate having an underlayer film; and

[0271] (b) Control for forming a metal-containing resist film on the underlayer film using a metal-containing precursor having a photosensitive group and a polyfunctional compound.

[0272] (Supplementary Note 21)

[0273] A method for manufacturing a device, comprising:

[0274] (a) A step of providing a substrate having an underlayer film; and

[0275] (b) A step of forming a metal-containing resist film on the underlayer film using a metal-containing precursor having a photosensitive group and a polyfunctional compound.

[0276] (Supplementary Note 22)

[0277] A program that causes a computer of a substrate processing system having one or more substrate processing devices and a control unit to perform the following control:

[0278] (a) Control for providing a substrate having an underlayer film; and

[0279] (b) Control of forming a metal-containing resist film on the bottom film using a metal-containing precursor and a polyfunctional compound having a photosensitive group.

[0280] (Supplementary Note 23)

[0281] A storage medium storing the program described in Supplementary Note 22.

[0282] (Supplementary Note 24)

[0283] A development method, comprising:

[0284] (a) A step of providing a substrate having a bottom film and a metal-containing resist on the bottom film;

[0285] (b) A step of exposing the metal-containing resist through an exposure mask to form an exposed first region and an unexposed second region in the metal-containing resist; and

[0286] (c) A step of selectively removing one of the first region and the second region,

[0287] The metal-containing resist in (a) contains a compound having a repeating unit represented by the following formula (1) in the molecule:

[0288] -(M-X-A-X)-(1)

[0289] (In the above formula (1), M represents Sn, Ti, Hf, Zr or In, X represents a divalent group derived from a terminal functional group of a polyol, a polythiol, a polycarboxylic acid, a polyisocyanate or a polyisothiocyanate, and A represents a divalent organic group having 2 or more and 10 or less carbon atoms).

[0290] (Supplementary Note 25)

[0291] An etching method, comprising:

[0292] (a) A step of providing a substrate having a bottom film and a metal-containing resist on the bottom film, wherein the metal-containing resist has at least one opening; and

[0293] (b) A step of etching the bottom film through the opening,

[0294] The metal-containing resist contains a compound having a repeating unit represented by the following formula (1) in the molecule:

[0295] -(M-X-A-X)-(1)

[0296] (In the above formula (1), M represents Sn, Ti, Hf, Zr, or In, X represents a divalent group derived from the terminal functional groups of polyols, polythiols, polycarboxylic acids, polyisocyanates, or polyisothiocyanates, and A represents a divalent organic group having 2 or more and 10 or less carbon atoms).

[0297] The above embodiments are described for illustrative purposes and are not intended to limit the scope of the present disclosure. Each embodiment can be variously modified without departing from the scope and gist of the present disclosure. For example, a part of the components in a certain embodiment can be added to other embodiments. Additionally, a part of the components in a certain embodiment can be replaced with the corresponding components of other embodiments.

Claims

1. A substrate processing method, comprising: (a) a step of providing a substrate having a bottom film; and (b) a step of forming a metal-containing resist film on the bottom film using a metal-containing precursor having a photosensitive group and a polyfunctional compound.

2. The substrate processing method according to claim 1, wherein, the metal-containing precursor contains a compound (α) having an amino group and / or an alkoxy group.

3. The substrate processing method according to claim 2, wherein, the compound (α) contains a compound (α1), and the compound (α1) contains at least one metal selected from the group consisting of Sn, Ti, Hf, Zr, and In.

4. The substrate processing method according to claim 3, wherein, the compound (α1) contains Sn.

5. The substrate processing method according to claim 1, wherein, The photosensitive group includes at least one group selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, and -CH x F y where x represents an integer from 0 to 2 and y represents an integer from 1 to 3.

6. The substrate processing method according to claim 2, wherein, the polyfunctional compound contains at least one compound (β) selected from the group consisting of polyols, polythiols, polycarboxylic acids, polyisocyanates, and polyisothiocyanates.

7. The substrate processing method according to claim 1, wherein, In the process of (b) above, at least one selected from the group consisting of H 2 O, H 2 O 2 、O 3 and O 2 is further used.

8. The substrate processing method according to claim 1, wherein, the step (b) includes: (b1) a step of supplying a gas containing the metal-containing precursor onto the bottom film to form a metal-containing precursor film; and (b2) a step of supplying a gas containing the polyfunctional compound onto the metal-containing precursor film to form the metal-containing resist film from the metal-containing precursor film.

9. The substrate processing method according to claim 8, wherein, the steps (b1) and (b2) are repeated multiple times.

10. The substrate processing method according to claim 1, wherein, the step (b) includes forming the metal-containing resist film using a mixed gas containing the metal-containing precursor and the polyfunctional compound.

11. The substrate processing method according to claim 1, wherein, the metal-containing precursor contains a metal complex, and the metal complex contains at least one metal selected from the group consisting of Sn, Ti, Hf, Zr, and In.

12. The substrate processing method according to claim 11, wherein, the polyfunctional compound contains at least one compound (β) selected from the group consisting of polyols, polythiols, polycarboxylic acids, polyisocyanates, and polyisothiocyanates.

13. The substrate processing method according to claim 11, wherein, the step (b) includes: a step of coating a solution containing the metal-containing precursor and the polyfunctional compound on the bottom film; and a step of heating the coated solution to form a metal-containing resist film.

14. The substrate processing method according to claim 1, wherein, the substrate processing method further includes: (c) a step of exposing the substrate after the step (b) to form an exposed first region and an unexposed second region in the metal-containing resist film; and (d) a step of developing the substrate to selectively remove the second region from the metal-containing resist film.

15. The substrate processing method according to claim 14, Among them, in the step (d), the second region is removed by a developing gas or a developing solution containing a weak acid.

16. The substrate processing method according to claim 15, wherein, the weak acid contains an organic acid with an acid dissociation constant pKa less than 16.

17. The substrate processing method according to claim 16, wherein, the organic acid contains at least one selected from the group consisting of alcohols, thiols, carboxylic acids, sulfonic acids, β-dicarbonyl compounds, alkyl carbonates, and azoles.

18. A composition for forming a metal-containing resist, comprising: a metal-containing precursor having a photosensitive group; and a polyfunctional compound, the metal-containing precursor contains a compound having a photosensitive group and an amino group and / or an alkoxy group.

19. A metal-containing resist, comprising a compound having a repeating unit represented by the following formula (1) in the molecule: -(M-X-A-X)-(1) In the above formula (1), M represents Sn, Ti, Hf, Zr, or In, X represents a divalent group derived from the terminal functional group of a polyol, a polythiol, a polycarboxylic acid, a polyisocyanate, or a polyisothiocyanate, and A represents a divalent organic group having 2 or more and 10 or less carbon atoms.

20. A substrate processing system, which is a substrate processing system having one or more substrate processing devices and a control unit, the control unit is configured to perform the following controls on the one or more substrate processing devices: (a) Control for providing a substrate having an underlayer film; and (b) Control for forming a metal-containing resist film on the underlayer film using a metal-containing precursor having a photosensitive group and a polyfunctional compound.

21. A developing method, comprising: (a) A step of providing a substrate having an underlayer film and a metal-containing resist on the underlayer film; (b) A step of exposing the metal-containing resist via an exposure mask to form an exposed first region and an unexposed second region in the metal-containing resist; and (c) A step of selectively removing one of the first region and the second region, the metal-containing resist in (a) contains a compound having a repeating unit represented by the following formula (1) in the molecule: -(M-X-A-X)-(1) In the above formula (1), M represents Sn, Ti, Hf, Zr, or In, X represents a divalent group derived from the terminal functional group of a polyol, a polythiol, a polycarboxylic acid, a polyisocyanate, or a polyisothiocyanate, and A represents a divalent organic group having 2 or more and 10 or less carbon atoms.

22. An etching method, comprising: (a) A step of providing a substrate having an underlayer film and a metal-containing resist on the underlayer film, wherein the metal-containing resist has at least one opening; and (b) A step of etching the underlayer film through the opening, the metal-containing resist contains a compound having a repeating unit represented by the following formula (1) in the molecule: -(M-X-A-X)-(1) In the above formula (1), M represents Sn, Ti, Hf, Zr, or In, X represents a divalent group derived from the terminal functional group of a polyol, a polythiol, a polycarboxylic acid, a polyisocyanate, or a polyisothiocyanate, and A represents a divalent organic group having 2 or more and 10 or less carbon atoms.

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