Substrate processing method and substrate processing apparatus

Abstract

In an exemplary embodiment, the substrate processing method includes: (a) providing a substrate on a substrate support portion in a chamber, the substrate including a film to be etched and a metal-containing resist on the film to be etched, the metal-containing resist having a first region exposed by EUV light and a second region not exposed by EUV light; and (b) a step of removing the second region by dry development using a developing gas, and after (b), the method includes: (c1) a step of generating a second metal-containing substance from the first metal-containing substance using a fluorine-containing gas, the second metal-containing substance including a metal fluoride; and (c2) a step for generating a third metal-containing substance from the second metal-containing substance by heating the chamber or the component and supplying a processing gas into the chamber, and removing the third metal-containing substance.

Description

Technical Field

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

[0002] Patent Document 1 discloses a method of plasma cleaning a mixed gas of boron trichloride and chlorine after etching a stacked film of an aluminum film and a titanium nitride film.

[0003] Prior Art Documents

[0004] Patent Documents

[0005] Patent Document 1: Japanese Unexamined Patent Application Publication No. 2000-12515 Summary of the Invention

[0006] Technical Problem to be Solved by the Invention

[0007] The present invention provides a substrate processing method and a substrate processing apparatus capable of suppressing damage to a chamber or components.

[0008] Means for Solving the Technical Problem

[0009] In one exemplary embodiment, a substrate processing method includes: (a) a step of providing a substrate on a substrate support portion in a chamber, wherein the substrate includes an etching target film and a metal-containing resist on the etching target film, and the metal-containing resist has a first region exposed to EUV light and a second region not exposed to EUV light; (b) a step of removing the second region by dry development using a developing gas; and (c) a step of removing a first metal-containing substance attached to a component in the chamber or in the chamber after (b), and the step (c) includes: (c1) a step of using a fluorine-containing gas to generate a second metal-containing substance from the first metal-containing substance, wherein the second metal-containing substance includes a metal fluoride; and (c2) a step of generating a third metal-containing substance from the second metal-containing substance by heating the chamber or the component and supplying a processing gas into the chamber, and removing the third metal-containing substance.

[0010] Advantageous Effects of the Invention

[0011] According to one exemplary embodiment, a technique capable of suppressing damage to a chamber or components is provided. Brief Description of the Drawings

[0012] Figure 1 is a diagram schematically showing a substrate processing apparatus according to an exemplary embodiment.

[0013] Figure 2It is a diagram schematically showing a substrate processing apparatus according to another exemplary embodiment.

[0014] Figure 3 It is a diagram schematically showing a substrate processing apparatus according to another exemplary embodiment.

[0015] Figure 4 It is a diagram schematically showing a substrate processing apparatus according to another exemplary embodiment.

[0016] Figure 5 It is a flowchart of a substrate processing method according to an exemplary embodiment.

[0017] Figure 6 It is applicable Figure 5 A cross-sectional view of a substrate which is an example of a method that can be applied.

[0018] Figure 7 It is a cross-sectional view showing one step of a dry development method according to an exemplary embodiment.

[0019] Figure 8 It is a partially enlarged cross-sectional view of a substrate processing apparatus which is an example after the development step.

[0020] Figure 9 It is a partially enlarged cross-sectional view of a substrate processing apparatus which is an example in the step of forming the second metal-containing substance.

[0021] Figure 10 It is a partially enlarged cross-sectional view of a substrate processing apparatus which is an example in the step of forming and removing the third metal-containing substance.

[0022] Figure 11 It is a flowchart of a substrate processing method according to a modification example. Detailed Description of the Invention

[0023] Hereinafter, various exemplary embodiments will be described in detail with reference to the accompanying drawings. In addition, in each drawing, the same or equivalent parts are denoted by the same reference numerals.

[0024] Figure 1 It is a diagram for explaining a structural example of a heat treatment system. In an exemplary embodiment, the heat treatment system includes a heat treatment apparatus 100 and a control unit 200. The heat treatment system is an example of a substrate processing system. The heat treatment apparatus 100 is an example of a substrate processing apparatus.

[0025] The heat treatment apparatus 100 has a processing chamber 102 (chamber) that is configured to be sealable. The processing chamber 102 is, for example, an airtight cylindrical container configured to be able to control the internal atmosphere. A side wall heater 104 is provided on the side wall of the processing chamber 102. A top wall 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, for example, a horizontal flat surface. The temperature of the top surface 140 is controlled by the top wall heater 130.

[0026] A substrate support portion 121 is provided on the lower side within the processing chamber 102. The substrate support portion 121 constitutes a mounting portion for mounting the substrate W. The substrate support portion 121 may have, for example, a circular surface (upper surface) or may have a horizontally formed surface (upper surface). The substrate W is mounted on the surface of the substrate support portion 121. A table heater 120 is embedded in the substrate support portion 121. The table heater 120 can heat the substrate W mounted on the substrate support portion 121. A ring assembly 125 may be arranged around the substrate W on the substrate support portion 121. The ring assembly 125 may include one or more ring-shaped members. By arranging the ring assembly 125, the temperature controllability of the outer peripheral region of the substrate W can be improved. The ring assembly 125 may be made of an inorganic material or an organic material according to the target heat treatment.

[0027] The substrate support portion 121 is supported in the processing chamber 102 by columns 122 provided on the bottom surface of the processing chamber 102. For example, a plurality of lift pins 123 that move vertically are provided on the outer side in the circumferential direction of the columns 122. The plurality of lift pins 123 are respectively inserted through a plurality of through holes provided at intervals in the circumferential direction of the substrate support portion 121. The lifting operation of the lift pins 123 is controlled by a lifting mechanism 124. When the lift pins 123 protrude from the surface of the substrate support portion 121, the substrate W is transferred between a transfer mechanism (not shown) and the substrate support portion 121.

[0028] An exhaust port 131 having an opening is provided on the side wall of the processing chamber 102. The exhaust port 131 is connected to an exhaust mechanism 132 via an exhaust pipe. The exhaust mechanism 132 is composed of a vacuum pump, a valve, etc., and adjusts the exhaust flow rate from the exhaust port 131. By adjusting the exhaust flow rate, etc. of the exhaust mechanism 132, the pressure inside the processing chamber 102 is adjusted. On the side wall of the processing chamber 102, a transfer port (not shown) for the substrate W is formed so as to be openable and closable at a position different from the position of the exhaust port 131.

[0029] Further, on the side wall of the processing chamber 102, a gas nozzle 141 is provided at a position different from the exhaust port 131 and the transfer port of 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 on the side opposite to the exhaust port 131.

[0030] The gas nozzle 141 is formed in a rod shape protruding from the side wall of the processing chamber 102 toward the center side of the processing chamber 102. The front end of the gas nozzle 141 extends horizontally from the side wall of the processing chamber 102, for example. The processing gas is ejected into the processing chamber 102 from the ejection port provided at the front end of the gas nozzle 141. The ejected processing gas flows along the Figure 1 direction of the arrow shown, and is discharged from the exhaust port 131. The front end of the gas nozzle 141 may extend obliquely downward toward the substrate W, or may extend obliquely upward toward the top surface 140 of the processing chamber 102.

[0031] The gas nozzle 141 may also be provided on the top wall of the processing chamber 102, for example. The exhaust port 131 may also be provided on the bottom surface of the processing chamber 102.

[0032] 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 inside of the gas supply pipe 152 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 gas source in a liquid state.

[0033] The control unit 200 processes computer-executable commands for causing the heat treatment apparatus 100 to execute the various processes described in the present invention. The control unit 200 can be configured to control each component of the heat treatment apparatus 100 in a manner that executes the various processes described herein. In one embodiment, part or all of the control unit 200 may be included in the heat treatment apparatus 100. The control unit 200 may include a processing unit 200a1, a storage unit 200a2, and a communication interface 200a3. The control unit 200 can be implemented, for example, by a computer 200a. The processing unit 200a1 can 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, and when needed, it may be obtained via a medium. The obtained program is stored in the storage unit 200a2 and is 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, or it may be a communication line connected to the communication interface 200a3. The processing unit 200a1 may be a CPU (Central Processing Unit). The storage unit 200a2 may include a RAM (Random Access Memory), a ROM (ReadOnly Memory), an HDD (Hard Disk Drive), an SSD (Solid State Drive), or a combination thereof. The communication interface 200a3 can communicate with the heat treatment apparatus 100 via a communication line such as a LAN (Local Area Network).

[0034] Figure 2 is a diagram schematically showing a substrate processing apparatus according to another exemplary embodiment. Figure 2 The illustrated heat treatment apparatus 101, in addition to Figure 1 the structure of the illustrated heat treatment apparatus 100, further includes a microwave heating device 50. The microwave heating device 50 can heat components (such as a substrate support portion 121 and a ring assembly 125) disposed in the processing chamber 102 or within the processing chamber 102.

[0035] The microwave heating device 50 may also include a microwave generation unit 51, a waveguide 52, and a quartz window 53. The microwave generation unit 51 is disposed outside the processing chamber 102, for example, above the processing chamber 102. The microwave generation unit 51 includes a magnetron that generates microwaves. The frequency of the microwaves is, for example, 2.45 GHz or 5.85 GHz. One end of the waveguide 52 is connected to the microwave generation unit 51. The other end of the waveguide 52 is connected to the quartz window 53. The quartz window 53 has a first surface connected to the waveguide 52 of the quartz window 53 and a second surface opposite to the first surface. The quartz window 53 is arranged such that the second surface is coplanar with the top surface 140 of the processing chamber 102. The microwaves generated in the microwave generation unit 51 are irradiated toward the processing chamber 102 or the substrate support 121 via the waveguide 52 and the quartz window 53. Thereby, the inner surface of the processing chamber 102 or the surface of the substrate support 121 is heated. The irradiation direction of the microwaves can be adjusted according to the position or orientation of the waveguide 52 and the quartz window 53.

[0036] The microwave heating device 50 may also heat the processing chamber 102 or the substrate support 121 by generating electromagnetic waves different from microwaves (for example, infrared rays). The microwave heating device 50 may also include an infrared lamp. The heat treatment device 101 may also include at least one of a side wall heater 104, a table heater 120, a top wall heater 130, or a pipe heater 160. Alternatively, the heat treatment device 101 may not include these heaters.

[0037] Figure 3 FIG. is a diagram illustrating a structural example when the plasma processing system is used as a developing processing system. In one embodiment, the plasma processing system includes a plasma processing device 1 and a control unit 2. The plasma processing system is an example of a substrate processing system, and the plasma processing device 1 is an example of a substrate processing device. The plasma processing device 1 includes a plasma processing chamber (hereinafter, simply referred to as "processing chamber") 10, a substrate support 11, and a plasma generation unit 12. The plasma processing chamber 10 has a plasma processing space. Further, 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 the gas from the plasma processing space. The gas supply port is connected to a gas supply unit 20 described later, and the gas discharge port is connected to an exhaust system 40 described later. The substrate support 11 is disposed in the plasma processing space and has a substrate support surface for supporting a substrate.

[0038] The plasma generation unit 12 is configured to generate plasma from at least one process gas supplied into the plasma processing space. The plasma formed in the plasma processing space may be capacitively coupled plasma (CCP), inductively coupled plasma (ICP), ECR plasma (Electron-Cyclotron-resonance plasma), helicon wave plasma (HWP), or surface wave plasma (SWP), etc. Also, various types of plasma generation units including an AC (Alternating Current) plasma generation unit and a DC (Direct Current) plasma generation unit may be used. In one embodiment, the AC signal (AC power) used in the AC plasma generation unit has a frequency in the range of 100 kHz to 10 GHz. Thus, the AC signal includes RF (Radio Frequency) signals and microwave signals. In one embodiment, the RF signal has a frequency in the range of 100 kHz to 150 MHz.

[0039] The control unit 2 processes computer-executable commands that cause the plasma processing apparatus 1 to perform the various processes described in the present invention. The control unit 2 can be configured to control each component of the plasma processing apparatus 1 in a manner that executes 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 can be implemented, for example, by a computer 2a. 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 (refer to Figure 1 ).

[0040] Hereinafter, a structural example of a capacitively coupled plasma processing apparatus as an example of the plasma processing apparatus 1 will be described. Figure 4 It is a diagram for explaining a structural example of a capacitively coupled plasma processing apparatus.

[0041] 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. Further, the plasma processing apparatus 1 includes a substrate support portion 11 and a gas introduction portion. The gas introduction portion is configured to introduce at least one processing gas into the plasma processing chamber 10. The gas introduction portion includes a showerhead 13. The substrate support portion 11 is disposed inside the plasma processing chamber 10. The showerhead 13 is disposed above the substrate support portion 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 portion 11. The plasma processing chamber 10 is grounded. The showerhead 13 and the substrate support portion 11 are electrically insulated from the housing of the plasma processing chamber 10.

[0042] The substrate support portion 11 includes a main body portion 111 and a ring assembly 112. The main body portion 111 has a central region 111a for supporting a substrate W and a ring-shaped region 111b for supporting the ring assembly 112. A wafer is an example of the substrate W. The ring-shaped 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 ring-shaped 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. Accordingly, the central region 111a is also referred to as a substrate support surface for supporting the substrate W, and the ring-shaped region 111b is also referred to as a ring support surface for supporting the ring assembly 112.

[0043] In one embodiment, the body portion 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 has an annular region 111b. Additionally, other components that surround the electrostatic chuck 1111, such as an annular electrostatic chuck or an annular insulating component, may also have an annular region 111b. In this case, the ring assembly 112 may be disposed on the annular electrostatic chuck or the annular insulating component, or may be disposed on both the electrostatic chuck 1111 and the annular insulating component. And at least one RF / DC electrode coupled to the RF power supply 31 and / or the DC power supply 32 described later may also be disposed within the ceramic component 1111a. In this case, the at least one RF / DC electrode functions as a lower electrode. When the bias RF signal and / or the 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 may also function as a plurality of lower electrodes. And the electrostatic electrode 1111b may also function as a lower electrode. Therefore, the substrate support portion 11 includes at least one lower electrode.

[0044] 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.

[0045] Moreover, the substrate support portion 11 may also include a temperature adjustment module configured to adjust at least one of the electrostatic chuck 1111, the ring assembly 112, and the substrate to a target temperature. The temperature adjustment module may also 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. And the substrate support portion 11 may also include a heat transfer gas supply portion configured to supply a heat transfer gas to the gap between the back surface of the substrate W and the central region 111a.

[0046] 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. Further, the showerhead 13 includes at least one upper electrode. In addition, the gas introduction unit may include, in addition to the showerhead 13, one or more side gas injectors (SGIs) mounted on one or more openings formed in the sidewall 10a.

[0047] The gas supply unit 20 may also 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 from their respective corresponding gas sources 21 to the showerhead 13 via their respective corresponding flow controllers 22. Each flow controller 22 may include, for example, a mass flow controller or a pressure-controlled flow controller. Further, the gas supply unit 20 may include at least one flow modulation device that modulates or pulses the flow rate of at least one processing gas.

[0048] The power supply 30 includes an RF power supply 31 coupled to the plasma processing chamber 10 via at least one impedance matching circuit. The RF power supply 31 is configured to supply at least one RF signal (RF power) to at least one lower electrode and / or at least one upper electrode. Thereby, a plasma is formed from at least one processing gas supplied to the plasma processing space 10s. Accordingly, the RF power supply 31 can function as at least a part of the plasma generation unit 12. Further, by supplying a bias RF signal to at least one lower electrode, a bias potential can be generated on the substrate W, and the ion component in the formed plasma can be introduced into the substrate W.

[0049] In one embodiment, the RF power supply 31 includes a first RF generation unit 31a and a second RF generation unit 31b. The first RF generation unit 31a is 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 RF signal (source RF power) for plasma generation. In one embodiment, the source RF signal has a frequency in the range of 10 MHz to 150 MHz. In one embodiment, the first RF generation unit 31a may be configured to generate a plurality of source RF signals having different frequencies. The generated one or more source RF signals are supplied to at least one lower electrode and / or at least one upper electrode.

[0050] The second RF generation unit 31b is configured to be coupled to at least one lower electrode via at least one impedance matching circuit and generate a bias RF signal (bias RF power). The frequency of the bias RF signal may be the same as or different from the frequency of the source RF signal. In one embodiment, the bias RF signal has a frequency lower than the frequency of the source RF signal. In one embodiment, the bias RF signal has a frequency in the range of 100 kHz to 60 MHz. In one embodiment, the second RF generation unit 31b may also be configured to generate a plurality of bias RF signals having different frequencies. The one or more generated bias RF signals are supplied to at least one lower electrode. Also, in various embodiments, at least one of the source RF signal and the bias RF signal may be pulsed.

[0051] Also, the power supply 30 may also include a DC power supply 32 coupled to the plasma processing chamber 10. The DC power supply 32 includes a first DC generation unit 32a and a second DC generation unit 32b. In one embodiment, the first DC generation unit 32a is configured to be connected to at least one lower electrode and generate a first DC signal. The generated first DC signal is applied to at least one lower electrode. In one embodiment, the second DC generation unit 32b is configured to be connected to at least one upper electrode and generate a second DC signal. The generated second DC signal is applied to at least one upper electrode.

[0052] In various embodiments, the first and second DC signals may also be pulsed. In this case, a sequence of voltage pulses is applied to at least one lower electrode and / or at least one upper electrode. The voltage pulses may also have a pulse waveform of a rectangle, trapezoid, triangle, or a combination thereof. In one embodiment, a waveform generation unit for generating a sequence of voltage pulses from a DC signal is connected between the first DC generation unit 32a and at least one lower electrode. Thus, the first DC generation unit 32a and the waveform generation unit constitute a voltage pulse generation unit. In the case where the second DC generation unit 32b and the waveform generation unit constitute a voltage pulse generation unit, the voltage pulse generation unit is connected to at least one upper electrode. The voltage pulses may also have a positive polarity or a negative polarity. Also, 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 generation units 32a, 32b may be additionally provided in addition to the RF power supply 31, or the first DC generation unit 32a may be provided in place of the second RF generation unit 31b.

[0053] The exhaust system 40 can be connected, for example, to a gas outlet 10e provided at the bottom of the plasma processing chamber 10. The exhaust system 40 may also include a pressure regulating valve and a vacuum pump. The pressure inside the plasma processing space 10s is adjusted by the pressure regulating valve. The vacuum pump may also include a turbomolecular pump, a dry pump, or a combination thereof.

[0054] Figure 5 is a flowchart of a substrate processing method (hereinafter referred to as "method MT1") according to an exemplary embodiment. Method MT1 can include steps ST1 to ST7. Steps ST1 to ST7 can be executed in sequence. Method MT1 may not include steps ST3 to ST5 and step ST7.

[0055] Method MT1 can be executed using any one of the above-described substrate processing systems (refer to Figures 1 to 4 ), or can be executed using two or more of these substrate processing systems. For example, method MT1 can be executed using a heat treatment system (refer to Figure 1 or Figure 2 ). Hereinafter, a case where the control unit 200 controls each part of the heat treatment apparatus 100 or the heat treatment apparatus 101 to execute method MT1 with respect to the first substrate W1 (refer to Figure 6 ) and the second substrate W2 (refer to Figure 8 ) will be described as an example.

[0056] Figure 6 is a diagram showing an example of the cross-sectional structure of the first substrate W1 provided in step ST1. The first substrate W1 includes a base film UF, an etching target film FL formed on the base film UF, and a metal-containing resist RM. The first substrate W1 can be used for the manufacture of semiconductor devices. Semiconductor devices include, for example, semiconductor memory devices such as DRAM or 3D-NAND flash memories. The etching target film FL can be, for example, a spin-on glass (SOG) film or a spin-on carbon (SOC) film.

[0057] The metal-containing resist RM can also be a resist film containing a metal. The metal-containing resist RM may also contain at least one selected from the group consisting of tin (Sn), hafnium (Hf), and titanium (Ti). The metal-containing resist RM can contain, for example, at least one selected from the group consisting of tin oxide, hafnium oxide, and titanium oxide, and may also contain an organic substance.

[0058] The metal-containing resist RM has a first region RM1 exposed to EUV light and a second region RM2 not exposed to EUV light.

[0059] (Step ST1)

[0060] First, in step ST1, as Figure 1 orFigure 2 As shown, a first substrate W1 of the substrate W is provided in the processing chamber 102 of the heat treatment apparatus 100. The first substrate W1 may also be conveyed into the processing chamber 102. The first substrate W1 is provided on the substrate support portion 121 via the lift pins 23. After the first substrate W1 is disposed on the substrate support portion 121, the temperature of the substrate support portion 121 is adjusted to a set temperature. Regarding the temperature adjustment of the substrate support portion 121, it can be performed by controlling the output of one or more of the side wall heater 104, the table heater 120, the top wall heater 130, and the pipe heater 160 (hereinafter, these heaters are collectively referred to as the "heater group"). In the method MT1, the temperature of the substrate support portion 121 can be adjusted to the set temperature before the process ST1. That is, after the temperature of the substrate support portion 121 is adjusted to the set temperature, the first substrate W1 can be provided on the substrate support portion 121.

[0061] (Process ST2)

[0062] Next, in the process ST2, as Figure 7 shown, the second region RM2 is removed by dry development using a developing gas. Specifically, by exposing the first substrate W1 to the developing gas, the second region RM2 of the first substrate W1 is selectively removed to develop the metal-containing resist RM. The developing gas is supplied into the processing chamber 102 through the gas supply unit 170. At the end of the process ST2, the supply of the developing gas can be stopped. In the process ST2, the first substrate W1 can also be heated.

[0063] In process ST2, at least one developing gas is supplied to the first substrate W1. The developing gas may also contain at least one selected from the group consisting of hydrogen bromide (HBr), hydrogen fluoride (HF), hydrogen chloride (HCl), boron trichloride (BCl3), organic acids (e.g., carboxylic acids, alcohols), and β-dicarbonyl compounds. The carboxylic acid in the developing gas may also contain, for example, at least one selected from the group consisting of formic acid (HCOOH), acetic acid (CH3COOH), trichloroacetic acid (CCl3COOH), monofluoroacetic acid (CFH2COOH), difluoroacetic acid (CF2FCOOH), trifluoroacetic acid (CF3COOH), chlorodifluoroacetic acid (CClF2COOH), sulfur-containing acetic acid, thioacetic acid (CH3COSH), mercaptoacetic acid (HSCH2COOH), trifluoroacetic anhydride ((CF3CO)2O), and acetic anhydride ((CH3CO)2O). The alcohol in the developing gas may contain, for example, nonafluorotert-butanol ((CF3)3COH). The β-dicarbonyl compound in the developing gas may be, for example, acetylacetone (CH3C(O)CH2C(O)CH3), trichloroacetylacetone (CCl3C(O)CH2C(O)CH3), hexachloroacetylacetone (CCl3C(O)CH2C(O)CCl3), trifluoroacetylacetone (CF3C(O)CH2C(O)CH3), hexafluoroacetylacetone (HFAc, CF3C(O)CH2C(O)CF3). In process ST2, development may also be performed by a thermal reaction between the developing gas and the metal-containing resist RM. Alternatively, development may be performed by a chemical reaction between chemical species of a plasma generated from the developing gas and the metal-containing resist RM.

[0064] In process ST2, one or more of the plurality of developing parameters may also be changed. The plurality of developing parameters include the temperature of the first substrate W1 or the substrate support portion 121, the pressure inside the processing chamber 102, the flow rate of the developing gas, the type of the developing gas, and the residence time of the developing gas with respect to the first substrate W1. One or more of these developing parameters may also be changed periodically. In one example, in process ST2, after setting the temperature of the substrate support portion 121 to a first temperature (e.g., 10 °C or higher and 30 °C or lower), it may be changed to a second temperature higher than the first temperature (e.g., 40 °C or higher and 100 °C or lower).

[0065] Process ST2 may be performed until the etching target film FL is exposed. Figure 7 is a diagram showing an example of the cross-sectional structure of the first substrate W1 after process ST2. In Figure 7In the example shown, the second region RM2 of the metal-containing resist RM is removed to form an opening OP. The opening OP is defined by the side surfaces of the first region RM1. When the first substrate W1 is viewed from above, the opening OP has a shape corresponding to the second region RM2 (eventually a shape corresponding to the exposure mask pattern for EUV exposure). This shape can be, for example, a circle, an ellipse, a rectangle, or a shape combining one or more of these. Multiple openings OP can be formed on the metal-containing resist RM. Each opening OP can have a line pattern or a hole pattern.

[0066] (Step ST3)

[0067] After step ST2, in step ST3, the first substrate W1 can also be transported from the transport port of the first substrate W1 to the outside of the processing chamber 102. Step ST3 can also be included between step ST2 and step ST6. Since step ST2 is performed in a state where the first substrate W1 is provided in the processing chamber 102, the first metal-containing substance MS1 can adhere to the surface of the first substrate W1. In step ST3, the first substrate W1 to which the first metal-containing substance MS1 is adhered can also be transported.

[0068] (Step ST4)

[0069] In step ST4, steps ST1, ST2, and ST3 can be repeated. Step ST4 can also be included between step ST2 and step ST6. Dry development can be sequentially performed on a plurality of first substrates W1 through step ST4. Alternatively, when dry development is performed on a single first substrate W1, step ST4 may not be performed.

[0070] (Step ST5)

[0071] After step ST4, in step ST5, as Figure 8 shown, a second substrate W2 different from the first substrate W1 can also be transported into the processing chamber 102. The second substrate W2 can also be a cleaning substrate (dummy wafer). In steps ST1, ST3 to ST5, for example, the substrates can be loaded and unloaded by a transfer robot.

[0072] Through the dry development in step ST2, as Figure 8 shown, the first metal-containing substance MS1 can adhere to the parts disposed in the processing chamber 102 or inside the processing chamber 102. Figure 8It is a partial enlarged cross-sectional view of a substrate processing apparatus in an example after process ST5. The first metal-containing substance MS1 can coat the inner surface of the processing chamber 102, the ring assembly 125, and the surface of the substrate support portion 121. The first metal-containing substance MS1 may contain the same metal as the metal contained in the metal-containing resist RM. The first metal-containing substance MS1 may also contain at least one selected from the group consisting of tin (Sn), hafnium (Hf), and titanium (Ti). The first metal-containing substance MS1 may contain at least one selected from the group consisting of tin oxide, hafnium oxide, and titanium oxide.

[0073] (Process ST6)

[0074] In process ST6, the first metal-containing substance MS1 attached to the processing chamber 102, the ring assembly 125, and the substrate support portion 121 is removed. Process ST6 may also be performed in a state where the second substrate W2 is disposed on the substrate support portion 121. Process ST6 includes process ST61 and process ST62 after process ST61.

[0075] (Process ST61)

[0076] First, in process ST61, as Figure 9 shown, using the fluorine-containing gas G1, the second metal-containing substance MS2 is generated from the first metal-containing substance MS1. Figure 9 It is a partial enlarged cross-sectional view of a substrate processing apparatus in an example in the process of generating the second metal-containing substance MS2. In process ST61, inside the processing chamber 102, using the fluorine-containing gas G1, the second metal-containing substance MS2 is generated from the first metal-containing substance MS1 attached to the processing chamber 102, the ring assembly 125, and the substrate support portion 121. The second metal-containing substance MS2 can coat the inner surface of the processing chamber 102, the ring assembly 125, and the surface of the substrate support portion 121. The fluorine-containing gas G1 is supplied from the gas supply unit 170 into the processing chamber 102. At the end of process ST61, the supply of the fluorine-containing gas G1 can be stopped. In process ST61, the second metal-containing substance MS2 may be generated using the fluorine-containing gas G1 without generating plasma.

[0077] The fluorine-containing gas G1 may also contain at least one selected from the group consisting of hydrogen fluoride gas (HF gas), fluorocarbon gas, hydrofluorocarbon gas, nitrogen fluoride gas, and sulfur fluoride gas. The fluorocarbon gas may also contain at least one selected from the group consisting of C4F6 gas, C4F8 gas, C3F8 gas, and CF4 gas. The hydrofluorocarbon gas may also contain at least one selected from the group consisting of CHF3 gas and CH2F2 gas. The nitrogen fluoride gas may also contain NF3 gas. The sulfur fluoride gas may also contain SF6 gas. The fluorine-containing gas G1 is supplied into the processing chamber 102 through the gas supply unit 170.

[0078] The second metal-containing substance MS2 can be formed by the reaction of the first metal-containing substance MS1 with the fluorine-containing gas G1. The second metal-containing substance MS2 can also contain the same metal as the metal contained in the first metal-containing substance MS1 and fluorine. The second metal-containing substance MS2 can also contain metal fluorides. In one example, the second metal-containing substance MS2 can also contain tin fluoride (SnF). The second metal-containing substance MS2 can also contain at least one selected from the group consisting of SnF4 and SnF2.

[0079] After the process ST61, a purification process can also be performed. In the purification process, after supplying a purification gas into the processing chamber 102, the purification gas is discharged. The purification gas is, for example, an inert gas such as nitrogen or argon.

[0080] (Process ST62)

[0081] As Figure 10 shown, in the process ST62, the processing chamber 102, the ring assembly 125, and the substrate support portion 121 are heated, and a processing gas G2 is supplied into the processing chamber 102. Thereby, the third metal-containing substance MS3 is formed from the second metal-containing substance MS2 to remove the third metal-containing substance MS3. Therefore, the first metal-containing substance MS1 attached to the processing chamber 102 or the parts can be removed. Figure 10 is a partial enlarged cross-sectional view of a substrate processing apparatus which is an example in the process of forming and removing the third metal-containing substance MS3.

[0082] The processing gas G2 can also contain a chlorine-containing gas. The processing gas G2 can also contain at least one selected from the group consisting of silicon tetrachloride gas (SiCl4 gas), titanium tetrachloride gas (TiCl4 gas), dimethylaluminum chloride gas (DMAC gas), thionyl chloride gas (SOCl2 gas), and acetyl chloride gas (CH3COCl gas). The processing gas G2 is supplied into the processing chamber 102 through the gas supply unit 170. At the end of the process ST62, the supply of the processing gas G2 can be stopped.

[0083] The third metal-containing substance MS3 can also contain tin chloride (SnCl). The third metal-containing substance MS3 can also contain at least one selected from the group consisting of SnCl3, SnCl4, and SnFCl3.

[0084] By controlling the output of more than one heater in the heater group, the components disposed in the processing chamber 102 or within the processing chamber 102 can also be heated. Alternatively, the components disposed in the processing chamber 102 or within the processing chamber 102 can be heated by controlling the microwave heating device 50, or can be heated by simultaneously controlling at least one in the heater group and the microwave heating device 50. The components disposed in the processing chamber 102 or within the processing chamber 102 can be heated to above 90 °C or above 120 °C, or can be heated to above 90 °C and below 300 °C.

[0085] The pressure within the processing chamber 102 in process ST62 can also be 100 mTorr (13 Pa) or more. By increasing the pressure, the supply amount of the processing gas G2 can be increased. Therefore, the cleaning speed can be improved.

[0086] In process ST62, the second metal-containing substance MS2 is modified by the processing gas G2, thereby generating a third metal-containing substance MS3 with high volatility. For example, through a ligand exchange reaction between a chlorine-containing gas and SnF, the F of SnF can be exchanged with Cl. As a result, highly volatile SnCl can also be generated. By heating, the generation of the third metal-containing substance MS3 from the second metal-containing substance MS2 and the volatilization (removal) of the third metal-containing substance MS3 are promoted.

[0087] (Process ST7)

[0088] In process ST7, the second substrate W2 can also be transported outside the processing chamber 102.

[0089] According to the above method MT1, compared with the case of using plasma generated from chlorine gas to remove the first metal-containing substance MS1 attached to the processing chamber 102 or the components, damage to the processing chamber 102 or the components caused by cleaning can be suppressed.

[0090] The metal-containing resist RM and the first metal-containing substance MS1 can contain tin. The second metal-containing substance MS2 can contain tin fluoride. The processing gas G2 can contain a chlorine-containing gas. The third metal-containing substance MS3 can contain tin chloride. In this case, through the ligand exchange reaction between the second metal-containing substance MS2 containing tin fluoride and the chlorine-containing gas, the third metal-containing substance MS3 containing tin chloride is generated. By the volatilization of the third metal-containing substance MS3, the third metal-containing substance MS3 can be removed.

[0091] In process ST62, the processing chamber 102, the ring assembly 125, and the substrate support portion 121 can also be heated to above 90 °C or above 120 °C. In this case, the reaction of generating the third metal-containing substance MS3 from the second metal-containing substance MS2 can be promoted.

[0092] Between process ST2 and process ST6, a process ST4 that repeatedly performs processes ST1 to ST3 may also be included. In this case, the throughput of process ST2 can be improved compared to the case where process ST6 is performed each time process ST2 is performed.

[0093] Process ST6 may also be performed in a state where a second substrate W2 different from the first substrate W1 is disposed on the substrate support portion 121. In this case, the substrate support portion 121 can be protected and process ST6 can be performed.

[0094] As described above, various exemplary embodiments have been described, but the present invention is not limited to the above-described exemplary embodiments, and various additions, omissions, substitutions, and changes can also be made. Moreover, components in different embodiments can be combined to form other embodiments.

[0095] Figure 11 It is a flowchart of a modified substrate processing method (hereinafter referred to as "method MT2"). Aspects in which method MT2 differs from method MT1 will be described. In method MT2, dry development using a developing gas containing a fluorine-containing gas may also be performed in process ST2. In method MT2, the first metal-containing substance MS1 may also contain metal fluoride. As Figure 11 shown, in method MT2, after process ST5, process ST63 may be performed as process ST6. In process ST63, the processing chamber 102 or components are heated, and a processing gas G2 is supplied into the processing chamber 102, whereby the second metal-containing substance MS2 can be generated from the first metal-containing substance MS1 and the second metal-containing substance MS2 can be removed. In this case, for example, in process ST2, by using a fluorine-containing gas in the developing gas, the first metal-containing substance MS1 can contain tin fluoride (SnF). Therefore, through a ligand exchange reaction between the first metal-containing substance MS1 containing tin fluoride and a chlorine-containing gas, the second metal-containing substance MS2 containing tin chloride can be generated. By volatilization of the second metal-containing substance MS2, the second metal-containing substance MS2 can be removed. In method MT2, process ST61 of method MT1 can be omitted.

[0096] In method MT1, as a developing processing system, Figure 3 and Figure 4 the plasma processing apparatus 1 shown can also be used. In process ST61, a plasma generated from a fluorine-containing gas G1 may also be used to generate the second metal-containing substance MS2. In this case, by plasmaizing the fluorine-containing gas G1, active species such as fluoride ions and fluorine radicals can be generated, for example.

[0097] Here, various exemplary embodiments included in the present invention are described in [E1] to [E13] below.

[0098] [E1]

[0099] A substrate processing method, comprising:

[0100] (a) a step of providing a substrate on a substrate support portion in a chamber, wherein the substrate has an etching target film and a metal-containing resist on the etching target film, and the metal-containing resist has a first region exposed by EUV light and a second region not exposed by EUV light;

[0101] (b) a step of removing the second region by dry development using a developing gas; and

[0102] (c) a step of removing a first metal-containing substance attached to a component in the chamber or in the chamber after (b),

[0103] The (c) includes:

[0104] (c1) a step of generating a second metal-containing substance from the first metal-containing substance using a fluorine-containing gas, wherein the second metal-containing substance contains metal fluoride; and

[0105] (c2) a step of generating a third metal-containing substance from the second metal-containing substance and removing the third metal-containing substance by heating the chamber or the component and supplying a processing gas into the chamber.

[0106] [E2]

[0107] The substrate processing method according to [E1], wherein,

[0108] The metal-containing resist and the first metal-containing substance contain tin,

[0109] The second metal-containing substance contains tin fluoride,

[0110] The processing gas contains a chlorine-containing gas,

[0111] The third metal-containing substance contains tin chloride.

[0112] [E3]

[0113] The substrate processing method according to [E1] or [E2], wherein,

[0114] The fluorine-containing gas contains at least one selected from the group consisting of hydrogen fluoride gas, fluorocarbon gas, hydrofluorocarbon gas, nitrogen fluoride gas, and sulfur fluoride gas.

[0115] [E4]

[0116] The substrate processing method according to any one of [E1] to [E3], wherein,

[0117] In (c1), the second metal-containing substance is generated using a plasma generated from the fluorine-containing gas.

[0118] [E5]

[0119] The substrate processing method according to any one of [E1] to [E3], wherein

[0120] In (c1), the second metal-containing substance is generated using hydrogen fluoride gas without generating a plasma.

[0121] [E6]

[0122] The substrate processing method according to [E2] or any one of [E3] to [E5] citing [E2], wherein

[0123] The chlorine-containing gas contains at least one selected from the group consisting of silicon tetrachloride gas, titanium tetrachloride gas, dimethylaluminum chloride gas, thionyl chloride gas, and acetyl chloride gas.

[0124] [E7]

[0125] The substrate processing method according to any one of [E1] to [E6], wherein

[0126] In (c2), the chamber or the part is heated to 90 °C or higher.

[0127] [E8]

[0128] The substrate processing method according to any one of [E1] to [E7], further comprising:

[0129] (d) Repeating the steps of (a) and (b) between (b) and (c).

[0130] [E9]

[0131] The substrate processing method according to any one of [E1] to [E8], further comprising:

[0132] (e) A step of transporting the substrate out of the chamber between (b) and (c).

[0133] [E10]

[0134] The substrate processing method according to [E9], wherein

[0135] The substrate is a first substrate,

[0136] (c) is performed in a state where a second substrate different from the first substrate is disposed on the substrate support portion.

[0137] [E11]

[0138] The substrate processing method according to any one of [E1] to [E10], wherein,

[0139] The developing gas contains at least one selected from the group consisting of hydrogen bromide gas, hydrogen fluoride gas, hydrogen chloride gas, boron trichloride gas, organic acid gas, and β-dicarbonyl compound gas.

[0140] [E12]

[0141] A substrate processing method, comprising:

[0142] (a) A step of providing a substrate on a substrate support portion in a chamber, wherein the substrate has an etching target film and a metal-containing resist on the etching target film, and the metal-containing resist has a first region exposed by EUV light and a second region not exposed by EUV light;

[0143] (b) A step of removing the second region by dry development using a developing gas containing a fluorine-containing gas; and

[0144] (c) After the step (b), a step of removing a first metal-containing substance attached to a part in the chamber or the chamber, wherein the first metal-containing substance contains metal fluoride,

[0145] The step (c) includes:

[0146] A step of generating a second metal-containing substance from the first metal-containing substance by heating the chamber or the part and supplying a processing gas into the chamber, and removing the second metal-containing substance.

[0147] [E13]

[0148] A substrate processing apparatus, comprising:

[0149] A chamber;

[0150] A substrate support portion for supporting a substrate in the chamber, the substrate having an etching target film and a metal-containing resist on the etching target film, and the metal-containing resist having a first region exposed by EUV light and a second region not exposed by EUV light;

[0151] A gas supply portion configured to supply a developing gas, a fluorine-containing gas, and a processing gas into the chamber respectively; and

[0152] A control portion,

[0153] The control portion is configured to control the gas supply portion to implement the following steps:

[0154] By dry developing using the developing gas, the second region is removed.

[0155] After removing the second region, the first metal-containing substance attached to the parts disposed in the chamber or within the chamber is removed.

[0156] In the process of removing the first metal-containing substance,

[0157] a fluorine-containing gas is used to generate a second metal-containing substance from the first metal-containing substance, and the second metal-containing substance contains metal fluoride.

[0158] By heating the chamber or the parts and supplying the processing gas into the chamber, a third metal-containing substance is generated from the second metal-containing substance, and the third metal-containing substance is removed.

[0159] Symbol Explanation

[0160] 1, 100, 101 - Substrate processing apparatus, 10, 102 - Chamber (processing chamber), 11, 121 - Substrate support portion, FL - Etching target film, G1 - Fluorine-containing gas, G2 - Processing gas, MS1 - First metal-containing substance, MS2 - Second metal-containing substance, MS3 - Third metal-containing substance, MT1 - Substrate processing method, RM - Metal-containing resist, RM1 - First region, RM2 - Second region, W - Substrate.

Claims

1. A substrate processing method, comprising: (a) A step of providing a substrate on a substrate support portion in a chamber, wherein the substrate has an etching target film and a metal-containing resist on the etching target film, and the metal-containing resist has a first region exposed by EUV light and a second region not exposed by EUV light; (b) A step of removing the second region by dry development using a developing gas; and (c) After the step (b), a step of removing a first metal-containing substance attached to a component in the chamber or in the chamber, The step (c) includes: (c1) A step of generating a second metal-containing substance from the first metal-containing substance using a fluorine-containing gas, wherein the second metal-containing substance contains metal fluoride; and (c2) A step of generating a third metal-containing substance from the second metal-containing substance and removing the third metal-containing substance by heating the chamber or the component and supplying a processing gas into the chamber.

2. The substrate processing method according to claim 1, wherein The metal-containing resist and the first metal-containing substance contain tin, The second metal-containing substance contains tin fluoride, The processing gas contains a chlorine-containing gas, The third metal-containing substance contains tin chloride.

3. The substrate processing method according to claim 1, wherein The fluorine-containing gas contains at least one selected from the group consisting of hydrogen fluoride gas, fluorocarbon gas, hydrofluorocarbon gas, nitrogen fluoride gas, and sulfur fluoride gas.

4. The substrate processing method according to claim 1, wherein In the step (c1), a plasma generated from the fluorine-containing gas is used to generate the second metal-containing substance.

5. The substrate processing method according to claim 1, wherein In the step (c1), the second metal-containing substance is generated using hydrogen fluoride gas without generating plasma.

6. The substrate processing method according to claim 2, wherein The chlorine-containing gas contains at least one selected from the group consisting of silicon tetrachloride gas, titanium tetrachloride gas, dimethylaluminum chloride gas, thionyl chloride gas, and acetyl chloride gas.

7. The substrate processing method according to claim 1, wherein In the step (c2), the chamber or the component is heated to 90 °C or higher.

8. The substrate processing method according to claim 1, further comprising: (d) Repeating the steps (a) and (b) between the step (b) and the step (c).

9. The substrate processing method according to claim 1, further comprising: (e) A step of transporting the substrate out of the chamber between the step (b) and the step (c).

10. The substrate processing method according to claim 9, wherein The substrate is a first substrate, The step (c) is performed in a state where a second substrate different from the first substrate is disposed on the substrate support portion.

11. The substrate processing method according to any one of claims 1 to 10, wherein The developing gas contains at least one selected from the group consisting of hydrogen bromide gas, hydrogen fluoride gas, hydrogen chloride gas, boron trichloride gas, organic acid gas, and β-dicarbonyl compound gas.

12. A substrate processing method, comprising: (a) a step of providing a substrate on a substrate support portion in a chamber, wherein the substrate has an etching target film and a metal-containing resist on the etching target film, and the metal-containing resist has a first region exposed by EUV light and a second region not exposed by EUV light; (b) a step of removing the second region by dry development using a developing gas containing a fluorine-containing gas; and (c) a step of removing a first metal-containing substance attached to a component disposed in the chamber or in the chamber after the step (b), wherein the first metal-containing substance contains metal fluoride, The step (c) includes: a step of generating a second metal-containing substance from the first metal-containing substance by heating the chamber or the component and supplying a processing gas into the chamber, and removing the second metal-containing substance.

13. A substrate processing apparatus, comprising: a chamber; a substrate support portion for supporting a substrate in the chamber, the substrate having an etching target film and a metal-containing resist on the etching target film, and the metal-containing resist having a first region exposed by EUV light and a second region not exposed by EUV light; a gas supply portion configured to supply a developing gas, a fluorine-containing gas, and a processing gas into the chamber respectively; and a control portion, The control portion is configured to control the gas supply portion to implement the following steps: removing the second region by dry development using the developing gas, after removing the second region, removing a first metal-containing substance attached to a component disposed in the chamber or in the chamber, in the step of removing the first metal-containing substance, using a fluorine-containing gas to generate a second metal-containing substance from the first metal-containing substance, the second metal-containing substance containing metal fluoride, generating a third metal-containing substance from the second metal-containing substance by heating the chamber or the component and supplying the processing gas into the chamber, and removing the third metal-containing substance.

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