Dry-type developing method and dry-type developing device

Abstract

The dry developing method of the present invention includes: (a) a step of providing a substrate on a substrate support portion in a chamber, the substrate including a base film and a metal-containing resist on the base film, the metal-containing resist having a first region that is exposed and a second region that is not exposed; (b) a step for forming a metal fluoride layer on the surface of the second region by supplying a first processing gas containing a fluorine-containing gas into the chamber; and (c) a step for removing the metal fluoride layer by supplying a second processing gas containing a chlorine-containing gas into the chamber.

Description

Technical Field

[0001] An exemplary embodiment of the present invention relates to a dry development method and a dry development apparatus. Background Art

[0002] Patent Document 1 discloses a technique for forming a metal-containing film on a semiconductor substrate that can be patterned using extreme ultraviolet light (hereinafter referred to as "EUV"). Patent Document 1 discloses a technique for selectively removing an unexposed area that has not been exposed to EUV using boron trichloride.

[0003] Prior Art Documents

[0004] Patent Documents

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

[0006] Technical Problem to be Solved by the Invention

[0007] The present invention provides a technique capable of appropriately developing a metal-containing resist.

[0008] Means for Solving the Technical Problem

[0009] In an exemplary embodiment, a dry development method includes: (a) a step of providing a substrate on a substrate support portion in a chamber, wherein the substrate includes a base film and a metal-containing resist on the base film, and the metal-containing resist has an exposed first region and an unexposed second region; (b) a step of forming a metal fluoride layer on the surface of the second region by supplying a first processing gas containing a fluorine-containing gas into the chamber; and (c) a step of removing the metal fluoride layer by supplying a second processing gas containing a chlorine-containing gas into the chamber.

[0010] Advantageous Effects of the Invention

[0011] According to an exemplary embodiment, a technique capable of appropriately developing a metal-containing resist is provided. Brief Description of the Drawings

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

[0013] Figure 2 is a diagram schematically showing a dry development apparatus according to another exemplary embodiment.

[0014] Figure 3 is a diagram schematically showing a dry development apparatus according to another exemplary embodiment.

[0015] Figure 4 is a flowchart of a dry development method according to an exemplary embodiment.

[0016] Figure 5 is applicable to Figure 4 a cross-sectional view of a substrate which is an example of a method.

[0017] Figure 6 is applicable to Figure 4 a cross-sectional view of a substrate which is another example of a method.

[0018] Figure 7 is applicable to Figure 4 a cross-sectional view of a substrate which is another example of a method.

[0019] Figure 8 is a cross-sectional view showing a process of a dry development method according to an exemplary embodiment.

[0020] Figure 9 is a cross-sectional view showing a process of a dry development method according to an exemplary embodiment.

[0021] Figure 10 is a cross-sectional view showing a process of a dry development method according to an exemplary embodiment.

[0022] Figure 11 is a diagram schematically showing a dry development apparatus according to another exemplary embodiment.

[0023] Figure 12 is a diagram schematically showing a dry development apparatus according to another exemplary embodiment.

[0024] Figure 13 is a diagram schematically showing a substrate support part according to another exemplary embodiment.

[0025] Figure 14 is a flowchart of a dry development method according to another exemplary embodiment.

[0026] Figure 15 is a diagram showing an example of control of the flow rate of a first processing gas and the flow rate of a second processing gas.

[0027] Figure 16 is a diagram showing another example of control of the flow rate of a first processing gas and the flow rate of a second processing gas.

[0028] Figure 17 is a flowchart of a dry development method according to another exemplary embodiment.

[0029] Figure 18It is a diagram schematically showing a substrate processing system according to an exemplary embodiment.

[0030] Figure 19 It is a flowchart of a substrate processing method according to an exemplary embodiment.

[0031] Figure 20 It is a chart showing an example of the result of the first experiment.

[0032] Figure 21 It is a chart showing an example of the result of the second experiment.

[0033] Figure 22 It is a chart showing an example of the result of the third experiment.

[0034] Figure 23 It is a table showing an example of the result of the fourth experiment. Detailed Embodiments

[0035] Hereinafter, various exemplary embodiments will be described in detail with reference to the accompanying drawings. In addition, in each of the drawings, the same or equivalent parts are denoted by the same reference numerals.

[0036] Figure 1 It is a diagram schematically showing a dry developing apparatus according to an exemplary embodiment. 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 dry developing system. The heat treatment apparatus 100 is an example of a dry developing apparatus.

[0037] The heat treatment apparatus 100 has a process chamber 102 (chamber) configured to be sealable. The process 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 process chamber 102. A top wall heater 130 is provided on the top wall (top plate) of the process chamber 102. The top surface 140 of the top wall (top plate) of the process chamber 102 is formed as a horizontal flat surface, for example. The temperature of the top surface 140 is controlled by the top wall heater 130.

[0038] A substrate support portion 121 is provided on the lower side within the processing chamber 102. The substrate support portion 121 constitutes a placement portion for placing 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 placed on the surface of the substrate support portion 121. A stage heater 120 is embedded in the substrate support portion 121. The stage heater 120 can heat the substrate W placed on the substrate support portion 121. A ring assembly 125 can be arranged on the substrate support portion 121 so as to surround the substrate W. 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.

[0039] The substrate support portion 121 is supported in the processing chamber 102 by a support column 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 support column 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 movement of the lift pins 123 is controlled by a lifting mechanism 124. When the lift pins 123 protrude from the surface of the substrate support portion 121, the substrate W is transferred between a transfer mechanism (not shown) and the substrate support portion 121.

[0040] 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 based on 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.

[0041] 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 on the opposite side of the exhaust port 131.

[0042] The gas nozzle 141 is formed in a rod shape protruding from the side wall of the processing chamber 102 toward the center of the processing chamber 102. The front end of the gas nozzle 141 extends horizontally from the side wall of the processing chamber 102, for example. The processing gas is ejected into the processing chamber 102 from an ejection port provided at the front end of the gas nozzle 141. The ejected processing gas flows along Figure 1It flows in the direction of the arrow AR1 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.

[0043] The gas nozzle 141 may also be provided, for example, on the top wall of the processing chamber 102. The exhaust port 131 may also be provided on the bottom surface of the processing chamber 102.

[0044] 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.

[0045] The control unit 200 processes computer-executable commands for causing the heat treatment apparatus 100 to perform 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 such a manner as 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 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, 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 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 StateDrive), or a combination thereof. The communication interface 200a3 may communicate with the heat treatment apparatus 100 via a communication line such as a LAN (Local Area Network).

[0046] Figure 2FIG. is a diagram schematically showing a dry developing apparatus according to another exemplary embodiment. In one embodiment, a plasma processing system includes a plasma processing apparatus 1 and a control unit 2. The plasma processing system is an example of a dry developing system, and the plasma processing apparatus 1 is an example of a dry developing apparatus. The plasma processing apparatus 1 includes a plasma processing chamber (hereinafter simply referred to as "processing chamber") 10, a substrate support unit 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 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 unit 11 is disposed in the plasma processing space and has a substrate support surface for supporting a substrate W.

[0047] The plasma generation unit 12 is configured to generate plasma from at least one processing gas supplied into the plasma processing space. The plasma formed in the plasma processing space may be 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 an RF (Radio Frequency) signal and a microwave signal. In one embodiment, the RF signal has a frequency in the range of 100 kHz to 150 MHz.

[0048] The control unit 2 processes computer-executable commands for causing 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 to execute 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 by, for example, a computer 2a. The control unit 2 may 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 ).

[0049] Hereinafter, a structural example of a capacitively coupled plasma processing apparatus as an example of the plasma processing apparatus 1 will be described. Figure 3 FIG. schematically shows a dry developing apparatus according to another exemplary embodiment.

[0050] 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 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 side wall 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.

[0051] 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 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. Therefore, 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.

[0052] 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 surrounding the electrostatic chuck 1111, such as an annular electrostatic chuck and an annular insulating component, may also have the 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 is 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.

[0053] 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.

[0054] 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.

[0055] 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 in one or more openings formed in the sidewall 10a.

[0056] 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.

[0057] 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.

[0058] 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.

[0059] 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. Further, in various embodiments, at least one of the source RF signal and the bias RF signal may be pulsed.

[0060] 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.

[0061] 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 such as rectangular, trapezoidal, triangular, 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 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 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 instead of the second RF generation unit 31b.

[0062] The exhaust system 40 can 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 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.

[0063] [First Embodiment]

[0064] Figure 4 is a flowchart of a dry developing method (hereinafter referred to as "Method MT1") according to an exemplary embodiment. As Figure 4 shown, Method MT1 has a step ST11 of providing a substrate W, a step ST12 of supplying a first processing gas, and a step ST13 of supplying a second processing gas. Method MT1 may also have a step ST14 of determining whether a stop condition is satisfied after step ST13. Method MT1 may also have a step ST15 of purifying the internal space of the chamber 102 between step ST12 and step ST13. Method MT1 may also have a step ST16 of purifying the internal space of the chamber 102 between step ST13 and step ST14. At least one of step ST15 and step ST16 may be implemented. Method MT1 may not include step ST15 and step ST16.

[0065] Method MT1 may also be implemented using any one of the above substrate processing systems (refer to Figures 1 to 3 ), or may be implemented using two or more of these substrate processing systems. For example, Method MT1 may be implemented by a heat treatment system (refer to Figure 1 ). Hereinafter, a case where the control unit 200 controls each part of the heat treatment apparatus 100 to implement Method MT1 on the substrate W will be described as an example.

[0066] (Step ST11: Provision of Substrate)

[0067] First, in step ST11, the substrate W is provided into the processing chamber 102 of the heat treatment apparatus 100. The substrate W is provided onto the substrate support portion 121, for example, by the lowering of 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 a set temperature. The temperature adjustment of the substrate support portion 121 may also 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. In Method MT1, the temperature of the substrate support portion 121 may also be adjusted to the set temperature before step ST11. That is, the substrate W may be provided onto the substrate support portion 121 after the temperature of the substrate support portion 121 is adjusted to the set temperature.

[0068] Figure 5 This is a cross-sectional view of a substrate W which is an example to which the method MT1 can be applied. The substrate W includes a base film UF and a metal-containing resist MF formed on the base film UF. The substrate W can also be used in the manufacture of semiconductor devices. Semiconductor devices include, for example, memory devices such as DRAM and 3D-NAND flash memories, and logic devices.

[0069] The metal-containing resist MF may also contain at least one selected from the group consisting of tin (Sn), hafnium (Hf), and titanium (Ti). The metal-containing resist MF may, for example, contain at least one selected from the group consisting of tin oxide, hafnium oxide, and titanium oxide, and may also contain an organic substance.

[0070] The metal-containing resist MF may also be an EUV resist. As Figure 5 shown, the metal-containing resist MF has an exposed first region MF1 and an unexposed second region MF2. The first region MF1 may also be an exposure region exposed by EUV exposure. The second region MF2 may also be an unexposed region not exposed by EUV exposure.

[0071] The base film UF may also be formed on a silicon wafer. The base film UF may also be a carbon-containing film, a dielectric film, a metal film, a semiconductor film, or a stacked film thereof.

[0072] Figure 6 and Figure 7 This is a cross-sectional view of another example of a substrate W to which the method MT1 can be applied. As Figure 6 shown, the base film UF may also be composed of a first film UF1, a second film UF2, and a third film UF3. And, as Figure 7 shown, the base film UF may also be composed of the second film UF2 and the third film UF3.

[0073] 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 a carbon-containing 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 may also be composed of a plurality of stacked silicon-containing films. For example, the third film UF3 may be formed by alternately stacking a silicon oxide film and a silicon nitride film. The third film UF3 may be formed by alternately stacking a silicon oxide film and a polysilicon film. The third film UF3 may also be a stacked film including a silicon nitride film, a silicon oxide film, and a polysilicon film. The third film UF3 may be formed by stacking a silicon oxide film and a silicon carbonitride film. The third film UF3 may also be a stacked film containing a silicon oxide film, a silicon nitride film, and a silicon carbonitride film.

[0074] In one embodiment, the substrate W is formed as follows. First, a metal-containing photoresist film is formed on a base film that has undergone adhesion treatment or the like. Film formation can be performed by a dry process, a wet process such as solution coating, or both a dry process and a wet process. Surface modification treatment of the base film can also be performed before film formation of the photoresist film. The wafer after film formation is subjected to a heat treatment, i.e., post apply bake (PAB). An additional heat treatment can also be performed after PAB. The wafer after heat treatment is transported to an exposure apparatus, and EUV is irradiated onto the photoresist film through an exposure mask (reticle). Thus, the substrate W is formed, which has a base film UF and a metal-containing resist MF having an exposed first region MF1 and an unexposed second region MF2. The first region MF1 is a region corresponding to the opening provided in the exposure mask (reticle). The second region MF2 is a region corresponding to the pattern provided in the exposure mask (reticle). EUV has a wavelength in the range of, for example, 10 nm to 20 nm. EUV can have a wavelength in the range of 11 nm to 14 nm and has a wavelength of 13.5 nm in one example. The wafer after exposure is transported from the exposure apparatus to a heat treatment apparatus under atmosphere management and is subjected to a heat treatment, i.e., post exposure bake (PEB). The wafer after exposure can also be further heat-treated after PEB.

[0075] (Process ST12: Supply of the first processing gas)

[0076] In the following description, the case of processing the Figure 5 shown substrate W is described. Figures 8 to 10 It is a cross-sectional view showing one process of a dry development method according to an exemplary embodiment.

[0077] Figure 8 It is a cross-sectional view of the substrate W in process ST12. In process ST12, by supplying a first processing gas containing a fluorine-containing gas into the processing chamber 10, as Figure 8 shown, a metal fluoride layer MF21 is formed on the surface of the second region MF2. In process ST12, fluorine contained in the fluorine-containing gas reacts with the metal (e.g., tin) present on the surface of the second region MF2 to form a metal fluoride layer MF21 (e.g., tin fluoride (SnF) layer). In Figure 8 the example of, the metal fluoride layer MF21 can also be formed without generating plasma. At the end of process ST12, the supply of the first processing gas can be stopped.

[0078] The fluorine-containing gas may also contain at least one selected from the group consisting of hydrogen fluoride gas (HF gas) and xenon fluoride gas (e.g., XeF2 gas). The first processing gas may also contain an inert gas. The inert gas may also contain a noble gas. The inert gas may also contain at least one selected from the group consisting of nitrogen gas (N2 gas), argon gas (Ar gas), xenon gas (Xe gas), and krypton gas (Kr gas).

[0079] In step ST12, the partial pressure of the fluorine-containing gas supplied into the processing chamber 10 can be controlled. The partial pressure of the fluorine-containing gas may be 13.3 Pa or more. The partial pressure of the fluorine-containing gas may be 13.3 kPa or less. The partial pressure of the fluorine-containing gas may be 13.3 Pa or more and 13.3 kPa or less. The partial pressure of the fluorine-containing gas may be 0.1 Torr or more. The partial pressure of the fluorine-containing gas may be 100 Torr or less. The partial pressure of the fluorine-containing gas may be 0.1 Torr or more and 100 Torr or less.

[0080] In step ST12, the substrate support portion 121 can also be heated. Step ST12 can be carried out in a state where the temperature of the substrate support portion 121 is set to the first temperature. The first temperature may be 0 °C or more. The first temperature may be 30 °C or more. The first temperature may be 100 °C or more. The first temperature may be 300 °C or less. The first temperature may be 30 °C or more and 300 °C or less.

[0081] (Step ST15: Purification)

[0082] After step ST12, a step of purifying the internal space of the chamber 102 may be carried out in step ST15. In step ST15, for example, an inert gas may be supplied into the chamber 102, and the gas in the chamber 102 may be discharged, etc. The inert gas may also contain at least one selected from the group consisting of nitrogen and argon.

[0083] (Step ST13: Supply of the second processing gas)

[0084] Figure 9 is a cross-sectional view of the substrate W in step ST13. After step ST12, in step ST13, by supplying a second processing gas containing a chlorine-containing gas into the processing chamber 10, as Figure 9 shown, the metal fluoride layer MF21 is removed. In step ST13, by the reaction of the chlorine-containing gas with the metal fluoride layer MF21, the metal fluoride layer MF21 can be selectively removed with respect to the first region MF1. In step ST13, through the exchange reaction between chlorine in the chlorine-containing gas and fluorine in the metal fluoride layer MF21, volatile metal chlorides can be generated. By carrying out step ST13, as Figure 9As shown, it is possible to form a recess RE on the substrate W. At the end of process ST13, the supply of the second processing gas can be stopped.

[0085] The chlorine-containing gas may 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 second processing gas may also contain an inert gas. The inert gas may also contain a noble gas. The inert gas may also contain at least one selected from the group consisting of nitrogen gas (N2 gas), argon gas (Ar gas), xenon gas (Xe gas), and krypton gas (Kr gas).

[0086] The pressure inside the processing chamber 10 in process ST13 may also be lower than the pressure inside the processing chamber in process ST12. In process ST13, it is possible to control the partial pressure of the chlorine-containing gas supplied into the processing chamber 10. The partial pressure of the chlorine-containing gas may be 13.3 Pa or more. The partial pressure of the chlorine-containing gas may be 13.3 kPa or less. The partial pressure of the chlorine-containing gas may be 13.3 Pa or more and 13.3 kPa or less. The partial pressure of the chlorine-containing gas may be 0.1 Torr or more. The partial pressure of the fluorine-containing gas may be 100 Torr or less. The partial pressure of the chlorine-containing gas may be 0.1 Torr or more and 100 Torr or less.

[0087] In process ST13, the substrate support portion 121 may also be heated. Process ST13 can be carried out in a state where the temperature of the substrate support portion 121 is set to the second temperature. The second temperature may be the same as the first temperature or may be higher than the first temperature. The second temperature may be 30 °C or more, or may be 100 °C or more. The second temperature may be 300 °C or less, or may be 200 °C or less. The second temperature may also be 30 °C or more and 300 °C or less.

[0088] (Process ST16: Purification)

[0089] After process ST13, a process of purifying the internal space of the chamber 102 may also be carried out in process ST16. In process ST16, for example, an inert gas may be supplied into the chamber 102 and the gas inside the chamber 102 may be discharged, etc. The inert gas may also contain at least one selected from the group consisting of nitrogen and argon.

[0090] The processes ST12 and ST13 can also be repeated in this order. That is, the method MT1 can also include a process (corresponding to the process ST14) of repeatedly performing the processes ST12 and ST13. In the process of repeatedly performing the processes ST12 and ST13, at least one of the processes ST15 and ST16 can also be repeated. The process of repeatedly performing the processes ST12 and ST13 can also be repeated a preset number of times. The process of repeatedly performing the processes ST12 and ST13 can also be repeated until the recess RE reaches the base film UF (until the base film UF is exposed). The process of performing each of the processes ST12 and ST13 once can also be regarded as one cycle. In this case, the thickness of the second region MF2 removed in each cycle in the direction from the metal-containing resist MF toward the base film UF can also be 5 nm or more and 20 nm or less.

[0091] The process of repeatedly performing the processes ST12 and ST13 can also include the following steps: changing at least one selected from the group consisting of the pressure in the chamber 102, the temperature of the substrate support portion 121, the processing time of the process ST12, and the processing time of the process ST13 according to the aspect ratio of the recess RE formed in the process ST13. For example, the process of repeatedly performing the processes ST12 and ST13 can also include the following steps: performing at least one of reducing the pressure in the chamber 102, reducing the temperature of the substrate support portion 121, shortening the processing time of the process ST12, and shortening the processing time of the process ST13 according to the increase in the aspect ratio of the recess RE formed in the process ST13.

[0092] In the method MT1, each time the processes ST12 and ST13 are repeatedly performed, the pressure in the chamber 102, the temperature of the substrate support portion 121, the processing time of the process ST12, and the processing time of the process ST13 (hereinafter sometimes referred to as each parameter) can be adjusted according to the aspect ratio of the recess RE. Each parameter can be adjusted according to the absolute value of the aspect ratio or according to the increase amount of the aspect ratio. For example, in the method MT1, each time the processes ST12 and ST13 are repeatedly performed, each parameter can be successively reduced by several percent to several tens of percent according to the increase in the aspect ratio of the recess RE. The adjustment of each parameter can also set a limit on the number of times.

[0093] For example, a table showing the relationship between the aspect ratio of the recess RE and each parameter can also be stored in the storage portion 200a2 of the control portion 200. The control portion 200 can also adjust each parameter according to the table stored in the storage portion 200a2.

[0094] (Process ST14: Judgment)

[0095] The method MT1 may also include a step ST14 of determining whether a stop condition is satisfied. The stop condition may be satisfied when the removal amount (depth of the concave portion RE) in the second region MF2 reaches a threshold value. The stop condition may be satisfied when the base film UF is exposed. The stop condition may be satisfied when the total processing time of the step ST12 and the step ST13 reaches a threshold value. The stop condition may be satisfied when the number of repetitions of the step ST12 and the step ST13 reaches a threshold value. In the step ST14, when the stop condition is not satisfied (step ST14: No), the steps ST12 and ST13 may be repeated again. In this case, in the method MT1, the processing conditions may be changed from the previous cycle for the next cycle. In the method MT1, for example, the partial pressure of the fluorine-containing gas and the partial pressure of the chlorine-containing gas may be changed. In the method MT1, for example, the temperature of the substrate support portion 121 may be changed, and the type of the noble gas may also be changed. In the method MT1, the above change contents may be appropriately combined. On the other hand, in the step ST14, when the stop condition is satisfied (step ST14: Yes), the method MT1 may be ended.

[0096] According to the method MT1, the second region MF2 can be selectively removed with respect to the first region MF1. Therefore, the metal-containing resist can be developed appropriately. Specifically, in the method MT1, the first region MF1 is removed at the first speed, whereas the second region MF2 can be removed at the second speed greater than the first speed. The first speed is, for example, 1 nm / cycle or less. The second speed is, for example, 2 nm / cycle or more and 10 nm / cycle or less. Therefore, the second region MF2 can be removed with respect to the first region MF1 at a higher selectivity (the ratio of the speed at which the second region MF2 is removed to the speed at which the first region MF1 is removed).

[0097] The mechanism by which the second region MF2 can be selectively removed with respect to the first region MF1 is speculated as follows, but is not limited thereto. The first region MF1 and the second region MF2 both contain, for example, a bond between tin and oxygen (Sn-O bond). When the first region MF1 and the second region MF2 are exposed to the fluorine-containing gas, the Sn-O bond is replaced by the Sn-F bond. The first region MF1 contains more Sn-O bonds than the second region MF2. In other words, in the first region MF1, the density of the Sn-O bonds per unit volume is relatively high. Therefore, the replacement of the Sn-O bond by the fluorine-containing gas in the second region MF2 can proceed to a deeper position more easily than in the first region MF1. Moreover, the number of organic ligands contained in the second region MF2 is larger than the number of organic ligands contained in the first region MF1. Therefore, the second region MF2 is more volatile than the first region MF1.

[0098] Moreover, in method MT1, the thickness of the metal fluoride layer MF21 formed in process ST12 saturates at a certain point in time. Therefore, the depth of the recess RE formed in process ST13 (the removal amount of the second region MF2) can be controlled. Therefore, according to method MT1, high in-plane uniformity is obtained with respect to the depth of the recess RE. That is, the difference in the depth of the recess RE at the center of the substrate W and the depth of the recess RE at the periphery of the substrate W can be reduced.

[0099] When plasma is not generated in process ST12, damage to the substrate W or the substrate support portion 121 can be suppressed as compared with the case of using plasma.

[0100] In process ST12, when the first temperature of the substrate support portion 121 is 30°C or higher, the reaction between the second region MF2 and the fluorine-containing gas is promoted.

[0101] The second temperature of the substrate support portion 121 in process ST13 may also be higher than the first temperature of the substrate support portion 121 in process ST12. In this case, the reaction between the metal fluoride layer MF21 and the chlorine-containing gas is promoted, and thus the removal of the metal fluoride layer MF21 is also promoted. For example, when the metal fluoride layer MF21 is a SnF layer, through the reaction between the 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 setting the temperature of the substrate support portion 121 to the second temperature, the reaction between the chlorine-containing gas and SnF and the volatilization of SnCl are promoted.

[0102] When method MT1 includes a process of repeatedly performing process ST12 and process ST13, the thickness of the second region MF2 removed in the direction from the metal-containing resist MF toward the base film UF can be increased.

[0103] The process of repeatedly performing process ST12 and process ST13 may also include the following steps: according to an increase in the aspect ratio of the recess RE formed in process ST13, at least one of reducing the pressure in the chamber 102, reducing the temperature of the substrate support portion 121, shortening the processing time of process ST12, and shortening the processing time of process ST13 is performed. The recess RE of the metal-containing resist MF is likely to be formed in an inverted cone shape in which the width becomes wider toward the bottom (toward the base film UF). In contrast, for example, by reducing the pressure in the chamber 102 according to an increase in the aspect ratio of the recess RE, the progress of dry development is suppressed. As a result, since the side walls of the recess RE are less likely to be cut, the side wall shape of the developed recess RE can be made close to vertical.

[0104] [Second Embodiment]

[0105] As a heat treatment system, it can also be used in place of Figure 1 the heat treatment apparatus 100 shown Figure 11 and Figure 12 the heat treatment apparatus 100a shown. Figure 11 And Figure 12 is a diagram schematically showing a dry developing apparatus according to another exemplary embodiment. Figure 11 is a schematic cross-sectional view showing a structural example of the heat treatment apparatus 100a. Figure 12 is a schematic plan view showing a structural example of the heat treatment apparatus 100a. The heat treatment apparatus 100a includes a showerhead 141a provided on the top of the processing chamber 102 and a plurality of gas nozzles 141b provided on the side wall of the processing chamber 102. The showerhead 141a can be configured to face the substrate support portion 121. The plurality of gas nozzles 141b can be arranged, for example, at equal intervals in the circumferential direction along the side wall of the processing chamber 102. The plurality of gas nozzles 141b may also include a first gas nozzle 141b1 and a second gas nozzle 141b2. The first gas nozzle 141b1 and the second gas nozzle 141b2 can be arranged alternately. The types of gases supplied into the processing chamber 102 from the showerhead 141a, the gas nozzle 141b1, and the gas nozzle 141b2 may be the same or different. The gas from the showerhead 141a is supplied into the processing chamber 102 in the direction of the arrow AR2 shown in Figure 11 . The gas from the gas nozzle 141b1 is supplied into the processing chamber 102 in the direction of the arrow AR3 shown in Figure 11 and Figure 12 . The gas from the gas nozzle 141b2 is supplied into the processing chamber 102 in the direction of the arrow AR4 shown in Figure 11 and Figure 12 . The flow rates of the gases supplied into the processing chamber 102 from the showerhead 141a, the gas nozzle 141b1, and the gas nozzle 141b2 may be the same or different. Heaters may also be arranged on the substrate support portion 121 and the side wall of the processing chamber 102. A gas exhaust port may also be arranged on the bottom surface of the processing chamber 102.

[0106] According to the heat treatment apparatus 100a, it is possible to easily control the gas density in the processing chamber 102 and improve the in-plane uniformity in the development of the metal-containing resist MF.

[0107] [Third Embodiment]

[0108] As the substrate support portion, it can also be used in place of Figure 1 the substrate support portion 121 shown Figure 13 the substrate support portion 121a shown. Figure 13 is a diagram schematically showing the substrate support portion 121a according to another exemplary embodiment.Figure 13 The substrate support portion 121a shown has a plurality of zones, and heater electrodes are provided in each zone. In Figure 13 the example shown, the substrate support portion 121a has zones Z1 to Z14. The heater electrodes of each of the zones Z1 to Z14 are configured to be able to supply power independently of each other. That is, the substrate support portion 121a is configured to be able to perform temperature control independently for each zone. Therefore, according to the substrate support portion 121a, the in-plane uniformity in the development of the metal-containing resist MF can be improved.

[0109] [Fourth Embodiment]

[0110] The method MT1 can also be implemented by the Figure 2 and Figure 3 shown plasma processing apparatus 1 instead of the heat treatment apparatus 100a. In this case, in the step ST12, a plasma generated from a first processing gas containing a fluorine-containing gas can also be used to generate the metal fluoride layer MF21. By plasmaizing the first processing gas containing a fluorine-containing gas, active species such as fluoride ions and fluorine radicals can be generated, for example. In the fourth embodiment, the fluorine-containing gas may also contain at least one selected from the group consisting of hydrogen fluoride gas (HF gas), xenon fluoride 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.

[0111] [Fifth Embodiment]

[0112] In the dry development method according to the fifth embodiment, before the start of development, parts inside the processing chamber 102 such as the side wall of the processing chamber 102 or the substrate support portion 121 (hereinafter also referred to as "parts inside the chamber") can also be pre-coated. The pre-coating can also be carried out by methods such as Atomic Layer Deposition (hereinafter also referred to as "ALD method") and Chemical Vapor Deposition (hereinafter also referred to as "CVD method"). Among the gases used to form the pre-coating layer, gases that can form a film resistant to the processing gas containing carboxylic acid can also be selected. For example, silicon-containing gases can also be used in the gases for forming the pre-coating layer. The silicon-containing gas can also contain at least one selected from the group consisting of aminosilane and SiCl4. In this case, a silicon oxide film can be formed as a pre-coating layer on the side wall of the processing chamber 102 or the parts inside the chamber. Thereby, corrosion of the side wall of the processing chamber 102 or the parts inside the chamber caused by the processing gas can be suppressed.

[0113] In the dry development method according to the fifth embodiment, instead of or together with the pre-coating layer, the side wall of the processing chamber 102 and the parts inside the chamber can be made of a material resistant to processing gases containing carboxylic acid and the like.

[0114] In the dry development method according to the fifth embodiment, the inside of the processing chamber 102 can also be cleaned after development. In this case, on the basis of heating the processing chamber 102 and the parts inside the chamber, a cleaning gas can be supplied into the processing chamber 102. As the cleaning gas, a gas containing hydrogen halide can also be used. The gas containing hydrogen halide can also contain at least one selected from the group consisting of hydrogen bromide gas (HBr gas) and hydrogen fluoride gas. The cleaning can also be carried out by Thermal Atomic Layer Etching (hereinafter also referred to as "thermal ALE method"). Thereby, metal oxides attached to the side wall of the processing chamber 102 and the parts inside the chamber during development can be removed.

[0115] [Sixth Embodiment]

[0116] In the dry development method according to the sixth embodiment, the base film UF can also be etched using the metal-containing resist MF developed by the method MT1 as a mask. The etching conditions of the base film UF can also be selected according to the film type of the base film UF, etc. The etching of the base film UF can also be carried out by Figure 3 the plasma processing apparatus 1 shown.

[0117] [Seventh Embodiment]

[0118] Figure 14It is a flowchart of a dry development method (hereinafter referred to as "Method MT2") according to another exemplary embodiment. Method MT2 has a step ST21 of providing a substrate W and a step ST22 of supplying a processing gas. Method MT2 may also have a step ST23 of determining whether a stop condition is satisfied after step ST22. The substrate W may be the same as the substrate W according to the first embodiment. The metal-containing resist MF is developed by Method MT2.

[0119] In Method MT2, in step ST22, the second region MF2 is removed by supplying a processing gas containing a fluorine-containing gas and a chlorine-containing gas into the processing chamber 102. In step ST22, a mixed gas containing a fluorine-containing gas and a chlorine-containing gas can be supplied as the processing gas. That is, in step ST22, a fluorine-containing gas and a chlorine-containing gas can be supplied simultaneously. In this case, a step of forming a metal fluoride layer MF21 on the surface of the second region MF2 by the fluorine-containing gas and a step of removing the metal fluoride layer MF21 by the chlorine-containing gas can be performed simultaneously. The types of gases contained in the fluorine-containing gas and the chlorine-containing gas may be the same as those in Method MT1.

[0120] In Method MT2, the ratio (F2 / F1) of the flow rate F2 of the chlorine-containing gas to the flow rate F1 of the fluorine-containing gas may also be adjusted appropriately. F2 / F1 may also be changed during the implementation of step ST22. In one embodiment, F2 / F1 may be changed appropriately according to the processing time of step ST22 or according to the aspect ratio of the recess RE formed in step ST22. For example, as the aspect ratio of the recess RE increases, the flow rates of the fluorine-containing gas and the chlorine-containing gas may be adjusted such that F2 / F1 increases, or the flow rates of the fluorine-containing gas and the chlorine-containing gas may be adjusted such that F2 / F1 decreases.

[0121] Step ST22 may also include a step of reducing the pressure in the chamber 102 according to the increase in the aspect ratio of the recess RE. Step ST22 may also include the following steps: changing at least one selected from the group consisting of the pressure in the chamber 102, the temperature of the substrate support portion 121, the processing time of step ST12, and the processing time of step ST13 according to the aspect ratio of the recess RE. For example, step ST22 may include the following steps: performing at least one of reducing the pressure in the chamber 102, reducing the temperature of the substrate support portion 121, shortening the processing time of step ST12, and shortening the processing time of step ST13 according to the increase in the aspect ratio of the recess RE.

[0122] Each parameter may be adjusted according to the absolute value of the aspect ratio or according to the increase amount of the aspect ratio. For example, in step ST22, the pressure in the chamber 102 may also be reduced according to the increase in the aspect ratio of the recess RE.

[0123] In method MT2, the flow rate of the fluorine-containing gas and the flow rate of the chlorine-containing gas can also be adjusted in a manner that periodically varies F2 / F1. Process ST22 can also include a first period and a second period following the first period. In this case, F2 / F1 in the first period can be greater than F2 / F1 in the second period, or can be less than F2 / F1 in the second period.

[0124] In process ST22, the temperature of the substrate support portion 121 can be controlled. Examples of the temperature of the substrate support portion 121 in process ST22 can also be the same as the examples of the temperature of the substrate support portion 121 in process ST12 or process ST13 of method MT1.

[0125] Method MT2 can also have a process ST23 for determining whether a stop condition is satisfied. Process ST23 can also be performed in the same manner as process ST14 of method MT1. The stop condition can be satisfied when the removal amount (depth of the recess RE) in the second region MF2 reaches a threshold value. The stop condition can be satisfied when the base film UF is exposed. The stop condition can be satisfied when the processing time of process ST22 reaches a threshold value. In process ST23, when the stop condition is not satisfied (process ST23: no), process ST22 can be repeated. In this case, in method MT2, the processing conditions can also be changed from the previous process ST22 to perform the next process ST22. In method MT2, for example, the partial pressure of the fluorine-containing gas and the partial pressure of the chlorine-containing gas can be changed. In method MT2, for example, the temperature of the substrate support portion 121 can be changed, or the type of rare gas can be changed. In method MT2, the above change contents can also be appropriately combined. On the other hand, in process ST23, when the stop condition is satisfied (process ST23: yes), method MT2 can also be ended.

[0126] [Eighth Embodiment]

[0127] Figure 15 It is a diagram showing an example of the control of the flow rate of the first processing gas and the flow rate of the second processing gas in method MT1. The process of repeatedly performing process ST12 and process ST13 of method MT1 can also include a first period P1 in which process ST12 is performed for a first processing time T1 and process ST13 is performed for a second processing time T2. The process of repeatedly performing process ST12 and process ST13 can also include a second period P2 after the first period P1. In the second period P2, process ST12 is performed for a third processing time T3 shorter than the first processing time T1, and process ST13 is performed for a fourth processing time T4 shorter than the second processing time T2.

[0128] In Figure 15In the example, during the first processing time T1, the flow rate of the first processing gas is at the Hi level (high level). On the other hand, the flow rate of the second processing gas is adjusted to the Low level (low level). Thus, during the first processing time T1, process ST12 is performed. The flow rate at the Hi level can also be greater than the flow rate at the Low level. The flow rate at the Low level can be 50% or less of the flow rate at the Hi level, or can be 20% or less. The flow rate at the Low level can also be zero. During the second processing time T2, the flow rate of the first processing gas is at the Low level, while the flow rate of the second processing gas is adjusted to the Hi level. Thus, during the second processing time T2, process ST13 is performed. During the third processing time T3, the flow rate of the first processing gas is at the Hi level, while the flow rate of the second processing gas is adjusted to the Low level. Thus, during the third processing time T3, process ST12 is performed. During the fourth processing time T4, the flow rate of the first processing gas is at the Low level, while the flow rate of the second processing gas is adjusted to the Hi level. Thus, during the fourth processing time T4, process ST13 is performed.

[0129] The length of the third processing time T3 can be 80% or less of the length of the first processing time T1, or can be 50% or less, or can be 20% or less. The length of the fourth processing time T4 can be 80% or less of the length of the second processing time T2, or can be 50% or less, or can be 20% or less.

[0130] In the method according to the eighth embodiment, with an increase in the aspect ratio of the concave portion RE, the progress of dry development is suppressed. As a result, since the side walls of the concave portion RE are less likely to be cut, the side wall shape of the concave portion RE after development can be made close to vertical. Also, when the second period P2 is performed at the end of dry development (when the bottom of the concave portion RE reaches the base film UF during the second period P2), the removal selectivity of the second region MF2 with respect to the base film UF can be improved.

[0131] [Embodiment 9]

[0132] Figure 16It is a diagram showing another example of controlling the flow rate of the first processing gas and the flow rate of the second processing gas in the representation method MT1. In the process of repeatedly performing process ST12 and process ST13 of method MT1, one of the first processing gas and the second processing gas may also be continuously supplied into the chamber 102. The other gas of the first processing gas and the second processing gas may also be supplied into the chamber 102 in an alternating manner of a high level flow rate (first gas flow rate) and a low level flow rate (second gas flow rate) less than the high level flow rate. For example, the other gas of the first processing gas and the second processing gas may also be intermittently supplied into the chamber 102. Or, both the first processing gas and the second processing gas may be supplied into the chamber 102 in an alternating manner of a high level flow rate and a low level flow rate.

[0133] In Figure 16 In the example, process ST12 is performed within the first processing time T1, and process ST13 is performed within the second processing time T2 after the first processing time T1. The low level flow rate may be 50% or less of the high level flow rate, or may be 20% or less. The low level flow rate may also be zero.

[0134] In Figure 16 In the example, within the first processing time T1, the first processing gas is continuously supplied into the chamber 102 at a high level. Within the second processing time T2, the second processing gas is supplied into the chamber 102 in an alternating manner of a high level flow rate and a low level flow rate. Not limited to this case, within the first processing time T1, the first processing gas may also be supplied into the chamber 102 in an alternating manner of a high level flow rate and a low level flow rate. Within the second processing time T2, the second processing gas may also be continuously supplied into the chamber 102 at a high level.

[0135] At least one of the first processing gas and the second processing gas may also be pulse-controlled by the control unit 200 in an alternating supply manner of a high level flow rate and a low level flow rate. The duty ratio of the pulse of the pulse control may also be 50%. Or, the duty ratio of the pulse of the pulse control may be 20% or more, or may be 70% or more.

[0136] In the method according to the ninth embodiment, compared with the case of continuously supplying both the first processing gas and the second processing gas, the gas consumption can be saved.

[0137] [Tenth Embodiment]

[0138] Figure 17 It is a flowchart of a dry development method (hereinafter referred to as "method MT3") according to another exemplary embodiment. Method MT3 may also be through Figure 2or Figure 3 is implemented by the plasma processing apparatus 1. Method MT3 may also have steps ST12A and ST12B instead of step ST12 in method MT1. Step ST12B may be performed after step ST12A or before step ST12A. In step ST12A, a first processing gas containing a fluorine gas may be supplied into the processing chamber 10 without generating plasma to form a metal fluoride layer MF21 on the surface of the second region MF2 (refer to Figure 8 ). In step ST12B, a plasma generated from the first processing gas containing a fluorine gas may be used to form the metal fluoride layer MF21. By plasmaizing the first processing gas containing a fluorine gas, active species such as fluoride ions and fluorine radicals can be generated, for example.

[0139] [Structural example of substrate processing system]

[0140] Figure 18 is a diagram schematically showing 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.

[0141] The first carrier station CS1 transfers the first carrier C1 in and out between systems outside the substrate processing system SS. The first carrier station CS1 has a stage provided with a plurality of first mounting plates ST1. The first carrier C1 is mounted on each first mounting plate ST1. The first carrier C1 has a frame capable of accommodating a plurality of substrates W therein. The first carrier C1 is mounted on each first mounting plate ST1 in a state of accommodating multiple substrates W or in an empty state without accommodating substrates W. In one example, the first carrier C1 is a FOUP (Front Opening Unified Pod).

[0142] The first carrier station CS1 transports the substrate W between the first carrier C1 and the first processing station PS1. On the first carrier station CS1, a first transfer device HD1 is provided in a manner located between the placement table and the first processing station PS1. A second transfer device HD2 is provided on the first processing station PS1. The first transfer device HD1 transports the substrate W between the first carrier C1 on each first placement plate ST1 and the second transfer device HD2 in the first processing station PS1. A load lock module may also be provided between the first carrier station CS1 and the first processing station PS1. The load lock module can switch the pressure inside the load lock module to atmospheric pressure or vacuum. "Atmospheric pressure" may be the pressure inside the first transfer device HD1. "Vacuum" refers to a pressure lower than atmospheric pressure, for example, a medium vacuum of 0.1 Pa to 100 Pa. The inside of the second transfer device HD2 may be atmospheric pressure or vacuum. The load lock module can, for example, also transport the substrate W from the first transfer device HD1 at atmospheric pressure to the second transfer device HD2 at vacuum. The load lock module can, for example, also transport the substrate W from the second transfer device HD2 at vacuum to the first transfer device HD1 at atmospheric pressure.

[0143] The first processing station PS1 performs various processes on the substrate W. In one embodiment, the first processing station PS1 includes a pre-processing module PM1, a resist film forming module PM2, and a first heat treatment module PM3 (hereinafter collectively referred to as "the first substrate processing module PMa"). The second transfer device HD2 in the first processing station PS1 transports the substrate W. The second transfer device HD2 transports the substrate W between the first substrate processing modules PMa. The second transfer device HD2 transports the substrate W between the first processing station PS1 and the first carrier station CS1, or between the first processing station PS1 and the first interface station IS1.

[0144] The pre-processing module PM1 performs pre-processing 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 or a high-precision temperature adjustment unit for precisely adjusting the temperature of the substrate W. In one embodiment, the pre-processing module PM1 includes a hydrophobization treatment unit for performing surface modification treatment on the substrate W. Each processing unit in the pre-processing module PM1 may also be configured in a state including a heat treatment device 100 (reference Figure 1 ) and a plasma processing device 1 (reference Figure 2 and Figure 3 ).

[0145] The resist film forming module PM2 forms a resist film 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. The dry coating unit may also include a CVD apparatus or an ALD (Atomic Layer Deposition) apparatus that chemically vapor-deposits the resist film on the substrate W. Alternatively, the dry coating unit may include a PVD (Physical Vapor Deposition) apparatus that physically vapor-deposits the resist film. The dry coating unit may also be a heat treatment apparatus 100 (refer to Figure 1 ) or a plasma processing apparatus 1 (refer to Figure 2 and Figure 3 ).

[0146] 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 solution coating.

[0147] In one embodiment, the resist film forming module PM2 includes both a wet coating unit and a dry coating unit.

[0148] The first heat treatment module PM3 performs heat treatment on the substrate W. In one embodiment, the first heat treatment module PM3 includes any one of the following units: a pre-baking (PAB) unit that performs heat treatment on the substrate W on which the resist film is formed; a temperature adjustment unit that adjusts the temperature of the substrate W; and a high-precision temperature adjustment unit that adjusts the temperature of the substrate W with high precision. These units may each have one or more heat treatment apparatuses. A plurality of heat treatment apparatuses may also be configured by stacking heat treatment apparatuses. The heat treatment apparatus may, for example, also be a heat treatment apparatus 100 (refer to Figure 1 ). The heat treatment may also be performed at a preset temperature using a preset gas.

[0149] The first interface station IS1 has a third transfer device HD3. The third transfer device HD3 transfers the substrate W between the first processing station PS1 and the exposure apparatus EX. The third transfer device HD3 has a housing for accommodating the substrate W. The third transfer device HD3 may also be configured to be able to control the temperature, humidity, pressure, etc. inside the housing.

[0150] The exposure apparatus EX exposes the resist film on the substrate W using an exposure mask (reticle). The exposure apparatus EX may, for example, also be an EUV exposure apparatus that uses EUV as a light source.

[0151] The second interface station IS2 has a fourth transfer device HD4. The fourth transfer device HD4 transfers the substrate W between the exposure device EX and the second processing station PS2. The fourth transfer device HD4 has a frame for accommodating the substrate W. The fourth transfer device HD4 can also be configured to control the temperature, humidity, pressure, etc. inside the frame.

[0152] 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 (hereinafter collectively referred to as the "second substrate processing module PMb"). The second processing station PS2 has a fifth transfer device HD5. The fifth transfer device HD5 transfers the substrate W. The fifth transfer device HD5 transfers the substrate W between the second substrate processing modules PMb. The fifth transfer device HD5 transfers the substrate W between the second processing station PS2 and the second carrier station CS2, or between the second processing station PS2 and the second interface station IS2.

[0153] The second heat treatment module PM4 performs heat treatment on the substrate W. The second heat treatment module PM4 may also include a post-exposure bake (PEB) unit for heating the exposed substrate W. The second heat treatment module PM4 may also include a temperature adjustment unit for adjusting the temperature of the substrate W. The second heat treatment module PM4 may also include a high-precision temperature adjustment unit for precisely adjusting the temperature of the substrate W. Alternatively, the second heat treatment module PM4 may include any one or more of these. These units may each have one or more heat treatment devices. The multiple heat treatment devices may also be constituted by stacking heat treatment devices. The heat treatment device may, for example, also be a heat treatment device 100 (refer to Figure 1 ). The heat treatment may be performed using a preset gas at a preset temperature.

[0154] The measurement module PM5 measures the substrate W. In one embodiment, the measurement module PM5 includes a stage for placing the substrate W, a photographing device, an illumination device, and a photographing unit including various sensors (temperature sensors, reflectance measurement sensors, etc.). The imaging device may, for example, also be a CCD camera for photographing the appearance of the substrate W, or a hyperspectral camera that spectrally analyzes and photographs for each wavelength. The hyperspectral camera can measure any one or more of the pattern shape, size, film thickness, composition, and film density of the resist film.

[0155] The development module PM6 performs a development process 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, for example, be a heat treatment device 100 (refer to Figure 1 ), or a plasma processing device 1 (refer to Figure 2 and Figure 3 ).

[0156] The third heat treatment module PM7 performs heat treatment on the substrate W. The third heat treatment module PM7 may also include a post-bake (PB) unit that heats the developed substrate W. The third heat treatment module PM7 may also include a temperature adjustment unit that adjusts the temperature of the substrate W. The third heat treatment module PM7 may also include a high-precision temperature adjustment unit that adjusts the temperature of the substrate W with high precision. Alternatively, the third heat treatment module PM7 may include any one or more of these. These units may each have one or more heat treatment devices. The plurality of heat treatment devices may also be configured by stacking heat treatment devices. The heat treatment device may be, for example, the heat treatment device 100 (refer to Figure 1 ). The heat treatment may be performed using a preset gas at a preset temperature.

[0157] The second carrier station CS2 carries in and out the second carrier C2 between systems outside the substrate processing system SS. The structure and function of the second carrier station CS2 may be the same as those of the above-described first carrier station CS1.

[0158] The control unit CT controls each structure of the substrate processing system SS and performs the above-described series of processes on the substrate W. The control unit CT stores a recipe in which the order of processes, process conditions, transfer conditions, etc. are set. The control unit CT controls each structure of the substrate processing system SS according to this recipe. The control unit CT may also have Figures 1 to 4 part or all of the functions of the respective control units (control unit 200, control unit 2, control unit 400) shown.

[0159] [An Example of a Substrate Processing Method]

[0160] Figure 19 is a flowchart of a substrate processing method (hereinafter referred to as "method MT4") according to an exemplary embodiment. As Figure 19As shown, method MT4 includes process ST100 to process ST900. Process ST100 is a process of performing pretreatment on the substrate. Process ST200 is a process of forming a resist film on the substrate W. Process ST300 is a process of performing a heat treatment (pre-baking: PAB) on the substrate W on which the resist film is formed. Process ST400 is a process of performing EUV exposure on the substrate W. Process ST500 is a process of performing a heat treatment (post-exposure baking: PEB) on the exposed substrate W. Process ST600 is a process of measuring the substrate W. Process ST700 is a process of developing the resist film on the substrate W. Process ST800 is a process of performing a heat treatment (post-baking: PB) on the developed substrate W. Process ST900 is a process of etching the substrate W. Method MT4 may not include one or more of the above processes. For example, method MT4 may not include process ST600, or process ST700 may be performed after process ST500.

[0161] Method MT4 may also use Figure 18 the substrate processing system SS shown below to implement. Hereinafter, an example will be described in which the control unit CT of the substrate processing system SS controls each part of the substrate processing system SS and executes method MT4 on the substrate W.

[0162] (Process ST100: Pretreatment)

[0163] 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 placement plate ST1. Then, by the first transfer device HD1, each substrate W in the first carrier C1 is sequentially taken out and transferred to the second transfer device HD2 in the first processing station PS1. The substrate W is transferred to the pretreatment module PM1 by the second transfer device HD2. The substrate W is pretreated by the pretreatment module PM1. The pretreatment may include, for example, one or more of temperature adjustment of the substrate W, formation of a part or all of the base film of the substrate W, heat treatment of the substrate W, and high-precision temperature adjustment of the substrate W. The pretreatment may also include surface modification treatment of the substrate W.

[0164] (Process S200: Resist Film Formation)

[0165] Next, the substrate W is transported to the resist film forming module PM2 by the second transport device HD2. Through the resist film forming module PM2, a resist film is formed on the substrate W. In one embodiment, the formation of the resist film is performed by a wet process such as a solution coating method. For example, the resist film is spin-coated on the substrate W by using the wet coating unit of the resist film forming module PM2, thereby forming the resist film. In one embodiment, the formation of the resist film on the substrate W is performed by a dry process such as a vapor deposition method. For example, the resist film is vapor-deposited on the substrate W by using the dry coating unit of the resist film forming module PM2, thereby forming the resist film.

[0166] 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 forming the first resist film on the substrate W by a dry process, the second resist film can be formed on the first resist film by a wet process. In this case, the film thickness, material, and composition of the first resist film can be the same as or different from those of the second resist film.

[0167] (Step ST300: PAB)

[0168] Next, the substrate W is transported to the first heat treatment module PM3 by the second transport device HD2. Through the first heat treatment module PM3, the substrate W is heat-treated (pre-baking: PAB). The pre-baking can be performed in an atmospheric atmosphere or in an inert atmosphere. In the pre-baking, the substrate W can be heated to 50°C or higher and 250°C or lower, or can be heated to 50°C or higher and 200°C or lower, or can also be heated to 80°C or higher and 150°C or lower. In the case where the resist film is formed by a dry process in Step ST200, the pre-baking can also be continuously performed by the dry coating unit that has performed Step ST200. In one embodiment, the process of removing the resist film at the end of the substrate W (edge bead removal: EBR) can also be performed after the pre-baking.

[0169] (Step ST400: EUV exposure)

[0170] Next, the substrate W is transferred to the third transport device HD3 in the first interface station IS1 by the second transport device HD2. And the substrate W is transported to the exposure apparatus EX by the third transport device HD3. The substrate W is EUV-exposed in the exposure apparatus EX via an exposure mask (reticle). Thereby, a first region that has been EUV-exposed and a second region that has not been EUV-exposed are formed on the substrate W corresponding to the pattern of the exposure mask (reticle).

[0171] (Step ST500: PEB)

[0172] Next, the substrate W is transported from the fourth transport device HD4 in the second interface station IS2 to the fifth transport device HD5 in the second processing station PS2. Then, the substrate W is transported by the fifth transport device HD5 to the second heat treatment module PM4 and subjected to a heat treatment (post-exposure bake: PEB). The post-exposure bake can also be carried out in an atmospheric atmosphere. In the post-exposure bake, the substrate W can also be heated to a temperature above 180°C and below 250°C.

[0173] (Process ST600: Measurement)

[0174] Next, the substrate W is transported by the fifth transport device HD5 to the measurement module PM5. The substrate W is measured by the measurement module PM5. The measurement can also be an optical measurement. In one embodiment, the measurement based on the measurement module PM5 includes the measurement of the appearance and dimensions of the substrate W using a CCD camera. In one embodiment, the measurement based on the measurement module PM5 includes the measurement of any one or more of the pattern shape, dimensions, film thickness, composition, and film density of the resist film (hereinafter also referred to as "pattern shape, etc.") using a hyperspectral camera.

[0175] 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 pattern shape, etc. of the substrate W. In one embodiment, when the control unit CT determines that there is an exposure abnormality of the substrate W, the development based on the process ST700 may not be performed, and the substrate W may be reworked or discarded. The rework of the substrate W can also be carried out by removing the resist on the substrate W and returning to the process ST200 to form a resist film again. By performing rework before development, damage to the substrate W can be avoided or suppressed.

[0176] (Process ST700: Development)

[0177] Next, the substrate W is transported by the fifth transport device HD5 to the development module PM6. In the development module PM6, the resist film of the substrate W is developed. The development process can also be carried out by dry development. The development process in the process ST700 can also be implemented by the method MT1 or the method MT2. One or more desorption processes can also be performed after or during the development process. The desorption process includes a process of removing scum from the surface of the resist film by an inert gas such as helium or a plasma of the inert gas, or a process of smoothing the surface. And, after the development process, the development module PM6 can also etch a part of the base film UF using the developed metal-containing resist MF as a mask.

[0178] (Process ST800: PB)

[0179] Next, the substrate W is transported to the third heat treatment module PM7 by the fifth transport device HD5 for heat treatment (post-baking). The post-baking can be carried out in an atmospheric atmosphere or in a reduced-pressure atmosphere containing N2 or O2. During the post-baking, the substrate W can also be heated to a temperature above 150°C and below 250°C. The post-baking can also 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. This measurement can be carried out in addition to or instead of the measurement in process ST600. In one embodiment, the control unit CT determines whether there are abnormalities such as defects in the developed pattern, scratches, and attachment of foreign substances on the substrate W based on the measured appearance, size, and pattern shape of the substrate W, etc. In one embodiment, when the control unit CT determines that the substrate W has an abnormality, the etching based on process ST900 may not be carried out, and the substrate W may be reworked or discarded. In one embodiment, when the control unit CT determines that the substrate W has an abnormality, the opening size of the resist film on the substrate W can also be adjusted by a dry coating unit (CVD device, ALD device, etc.).

[0180] (Process ST900: Etching)

[0181] After the implementation of process ST800, the substrate W is transported to the sixth transport device HD6 in the second carrier station CS2 by the fifth transport device HD5, and is transported to the second carrier C2 of the second carrier plate ST2 by the sixth transport device HD6. Then, the second carrier C2 is transported to a plasma processing system (not shown). In the plasma processing system, the developed resist film is used as a mask to etch the base film UF of the substrate W. Thus, the method MT3 ends. In addition, in process ST700, when the resist film is developed using a plasma processing device, the etching can also be continuously carried out in the plasma processing chamber of the same plasma processing device as the development. When the second processing station PS2 has a plasma processing module in addition to the development module PM6, the etching can also be carried out in the plasma processing module provided in the second processing station PS2. The above-described desorption treatment can be carried out one or more times before or during the etching.

[0182] Hereinafter, various experiments conducted to evaluate the methods MT1 to MT3 will be described. The experiments described below do not limit the present invention.

[0183] (First Experiment)

[0184] In the first experiment, on the substrate support part in the chamber, there was prepared a substrate having the same shape as Figure 6A substrate having the same structure as the substrate W shown. The metal-containing resist MF is an EUV resist and contains tin (Sn). The first film UF1 is a SOG film. The second film UF2 is a SOC film. The third film UF3 is a silicon oxide film.

[0185] Then, without generating plasma, the first processing gas is supplied into the chamber (step ST12). The first processing gas is a mixed gas of hydrogen fluoride gas (HF gas) and argon gas. The pressure in the chamber is 106.7 Pa (0.8 Torr). The partial pressure of the hydrogen fluoride gas is 88.9 Pa (0.67 Torr). The temperature of the substrate support is 120 °C.

[0186] Then, without generating plasma, the second processing gas is supplied into the chamber (step ST13). The second processing gas is a mixed gas of silicon tetrachloride gas (SiCl4 gas) and argon gas. The pressure in the chamber is 26.7 Pa (0.2 Torr). The partial pressure of the silicon tetrachloride gas is 2.4 Pa (0.02 Torr). The temperature of the substrate support is 120 °C.

[0187] Then, steps ST12 and ST13 are repeated in such a way that steps ST12 and ST13 are each performed 5 times. The number of times steps ST12 and ST13 are each performed is defined as the number of cycles.

[0188] (The Second Experiment)

[0189] The second experiment was conducted in the same manner as the first experiment, except that step ST13 was not performed and the steps were repeated. The processing time of step ST12 was 240 seconds.

[0190] (The Third Experiment)

[0191] The third experiment was conducted in the same manner as the first experiment, except that step ST12 was not performed and the steps were repeated. The processing time of step ST13 was 240 seconds.

[0192] (Results of the First Experiment)

[0193] Figure 20 is a chart showing an example of the results of the first experiment. In Figure 20 , the horizontal axis represents the number of cycles, and the vertical axis represents the film thicknesses of the first region MF1 and the second region MF2. From Figure 20 , it can be seen that the film thickness of the second region MF2 decreases as the number of cycles increases and becomes 0 nm in the fourth cycle. From this result, it can be known that the dry development does not stop halfway and can completely remove the second region MF2. Figure 20The dashed lines in [the figure] are approximate straight lines of the results of the first region MF1 and the second region MF2, respectively. Based on the approximate straight lines, the film thickness removed in each cycle of the first region MF1 and the second region MF2 is calculated. The film thickness removed from the first region MF1 in each cycle is 0.8 nm / cycle. The film thickness removed from the second region MF2 in each cycle is 9 nm / cycle. From this result, it can be seen that the second region MF2 can be removed with a high selectivity relative to the first region MF1.

[0194] (Results of the second experiment)

[0195] Figure 21 is a diagram showing an example of the results of the second experiment. In Figure 21 , the horizontal axis represents the time of supplying the processing gas, and the vertical axis represents the film thicknesses of the first region MF1 and the second region MF2. From Figure 21 , it can be seen that the film thickness of the second region MF2 decreases around 30 seconds from the start of supplying the processing gas, but then slowly increases. That is, it can be seen that without performing the process ST13, the dry development stops halfway and the second region MF2 cannot be completely removed.

[0196] (Results of the third experiment)

[0197] Figure 22 is a diagram showing an example of the results of the third experiment. From Figure 22 , it can be seen that the film thickness of the second region MF2 decreases around 120 seconds from the start of supplying the processing gas, but then slowly increases. That is, it can be seen that without performing the process ST12, the dry development stops halfway and the second region MF2 cannot be completely removed.

[0198] (The fourth experiment)

[0199] In the fourth experiment, a substrate having a metal-containing resist MF with a first region MF1 and a second region MF2 was prepared. The first region MF1 and the second region MF2 each had a line pattern in a top view. Then, a step of supplying a mixed gas of hydrogen fluoride gas and argon gas to the substrate was performed for 20 seconds. Then, a step of supplying a mixed gas of silicon tetrachloride gas and argon gas to the substrate was performed for 20 seconds. In the fourth experiment, when these two steps constituted one cycle, the number of cycles could be set from 1 to 6. The temperature of the substrate support portion could be set at intervals of 20°C between 60°C and 120°C. In the fourth experiment, dry development was performed on the basis of setting the number of cycles and the temperature of the substrate support portion. Then, for the developed substrate, the width (LCD: Line Critical Dimension) of the line pattern of the remaining first region MF1 and the deviation (LWR: Line Width Roughness) of the width of the line pattern of the first region MF1 were measured.

[0200] (Results of the Fourth Experiment)

[0201] Figure 23 is a table showing an example of the results of the fourth experiment. In Figure 23 , the horizontal item represents the number of cycles, and the vertical item represents the temperature of the substrate support portion. For example, the measured values of LCD and LWR shown in the upper leftmost part represent the values measured under the conditions that the number of cycles is one cycle and the temperature of the substrate support portion is 120°C. It can be seen from Figure 23 that if the temperature of the substrate support portion is low, the value of LCD becomes larger and the value of LWR becomes smaller. Also, it can be seen that under the condition that the temperature of the substrate support portion is 60°C, even if the number of cycles is increased, the decrease in the LCD value and the increase in the LWR value can be suppressed.

[0202] Here, various exemplary embodiments included in the present invention are described in the following [E1] to [E23].

[0203] [E1]

[0204] A dry development method, comprising:

[0205] (a) A step of providing a substrate on a substrate support portion in a chamber, wherein the substrate includes a base film and a metal-containing resist on the base film, and the metal-containing resist has a first region that has been exposed and a second region that has not been exposed;

[0206] (b) A step of forming a metal fluoride layer on the surface of the second region by supplying a first processing gas containing a fluorine-containing gas into the chamber; and

[0207] (c) A step of removing the metal fluoride layer by supplying a second processing gas containing a chlorine-containing gas into the chamber.

[0208] [E2]

[0209] The dry development method according to [E1], wherein

[0210] The metal-containing resist contains at least one selected from the group consisting of tin, hafnium, and titanium.

[0211] [E3]

[0212] The dry development method according to [E1] or [E2], wherein

[0213] The metal-containing resist is an EUV resist.

[0214] [E4]

[0215] The dry development method according to any one of [E1] to [E3], wherein

[0216] In the step (b), the metal fluoride layer is formed without generating plasma.

[0217] [E5]

[0218] The dry development method according to [E4], wherein

[0219] The fluorine-containing gas contains at least one selected from the group consisting of hydrogen fluoride gas and xenon fluoride gas.

[0220] [E6]

[0221] The dry development method according to any one of [E1] to [E5], wherein

[0222] In the step (b), the metal fluoride layer is formed using the plasma generated from the fluorine-containing gas.

[0223] [E7]

[0224] The dry development method according to [E6], wherein

[0225] The fluorine-containing gas contains at least one selected from the group consisting of hydrogen fluoride gas, xenon fluoride gas, nitrogen fluoride gas, fluorocarbon gas, hydrofluorocarbon gas, and sulfur fluoride gas.

[0226] [E8]

[0227] The dry development method according to any one of [E1] to [E7], wherein

[0228] In (b) above, the temperature of the substrate support portion is 30°C or higher.

[0229] [E9]

[0230] The dry development method according to any one of [E1] to [E8], wherein

[0231] 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.

[0232] [E10]

[0233] The dry development method according to any one of [E1] to [E9], wherein

[0234] In (c) above, the temperature of the substrate support portion is 30°C or higher.

[0235] [E11]

[0236] The dry development method according to any one of [E1] to [E10], further comprising:

[0237] (d) Repeating the steps of (b) and (c).

[0238] [E12]

[0239] The dry development method according to [E11], wherein

[0240] (d) includes the following steps:

[0241] According to the aspect ratio of the recess formed in the metal-containing resist in (c), at least one selected from the group consisting of the pressure in the chamber, the temperature of the substrate support portion, the processing time of (b), and the processing time of (c) is changed.

[0242] [E13]

[0243] The dry development method according to [E11] or [E12], wherein

[0244] (d) includes the following steps:

[0245] According to the increase in the aspect ratio of the recess formed in the metal-containing resist in (c), at least one of reducing the pressure in the chamber, reducing the temperature of the substrate support portion, shortening the processing time of (b), and shortening the processing time of (c) is performed.

[0246] [E14]

[0247] The dry development method according to any one of [E11] to [E13], wherein,

[0248] The (d) includes:

[0249] In the first period, the (b) is performed for a first processing time, and the (c) is performed for a second processing time; and

[0250] In the second period, after the first period, the (b) is performed for a third processing time shorter than the first processing time, and the (c) is performed for a fourth processing time shorter than the second processing time.

[0251] [E15]

[0252] The dry development method according to any one of [E11] to [E14], wherein,

[0253] In the (d),

[0254] One of the first processing gas and the second processing gas is continuously supplied into the chamber,

[0255] The other of the first processing gas and the second processing gas is supplied into the chamber in such a manner that a first gas flow rate and a second gas flow rate smaller than the first gas flow rate are alternated.

[0256] [E16]

[0257] The dry development method according to any one of [E1] to [E15], wherein,

[0258] The (b) includes:

[0259] A step of forming the metal fluoride layer without generating plasma; and

[0260] A step of generating plasma from the first processing gas to form the metal fluoride layer.

[0261] [E17]

[0262] The dry development method according to any one of [E1] to [E16], wherein,

[0263] After at least one of the (b) and the (c), it includes a step of purifying the internal space of the chamber.

[0264] [E18]

[0265] The dry development method according to any one of [E1] to [E17], wherein,

[0266] In each cycle including the step (b) and the step (c), the thickness of the second region removed in the direction from the metal-containing resist toward the base film is 5 nm or more and 20 nm or less.

[0267] [E19]

[0268] The dry development method according to any one of [E1] to [E18], wherein

[0269] the partial pressure of the chlorine-containing gas is 13.3 Pa or more and 13.3 kPa or less.

[0270] [E20]

[0271] The dry development method according to any one of [E1] to [E19], wherein

[0272] the step (b) is carried out at a first temperature,

[0273] the step (c) is carried out at a second temperature higher than the first temperature.

[0274] [E21]

[0275] A dry development method, comprising:

[0276] (a) a step of providing a substrate on a substrate support portion in a chamber, wherein the substrate includes a base film and a metal-containing resist on the base film, and the metal-containing resist has an exposed first region and an unexposed second region; and

[0277] (b) a step of removing the second region by supplying a processing gas containing a fluorine-containing gas and a chlorine-containing gas into the chamber.

[0278] [E22]

[0279] The dry development method according to [E21], wherein

[0280] the step (b) includes the step of reducing the pressure in the chamber according to an increase in the aspect ratio of the recess formed in the metal-containing resist.

[0281] [E23]

[0282] A dry development apparatus, comprising:

[0283] a chamber;

[0284] a substrate support portion for supporting a substrate in the chamber, the substrate including a base film and a metal-containing resist on the base film, and the metal-containing resist having an exposed first region and an unexposed second region;

[0285] A gas supply unit configured to supply a first processing gas containing a fluorine-containing gas and a second processing gas containing a chlorine-containing gas into the chamber; and

[0286] A control unit,

[0287] The control unit is configured to,

[0288] By supplying the first processing gas into the chamber, a metal fluoride layer is formed on the surface of the second region,

[0289] By supplying the second processing gas into the chamber, the metal fluoride layer is removed to control the gas supply unit.

[0290] Symbol Explanation

[0291] 1, 100 - Dry developing apparatus, 10, 102 - Chamber (processing chamber), 11, 121 - Substrate support part, 2, 200 - Control unit, 20, 170 - Gas supply unit, UF - Base film, MF - Metal-containing resist, MF1 - First region, MF2 - Second region, MF21 - Metal fluoride layer, MT1, MT2, MT3 - Dry developing method, W - Substrate.

Claims

1. A dry development method, comprising: (a) a step of providing a substrate on a substrate support portion in a chamber, wherein the substrate includes a base film and a metal-containing resist on the base film, and the metal-containing resist has an exposed first region and an unexposed second region; (b) a step of forming a metal fluoride layer on the surface of the second region by supplying a first processing gas containing a fluorine-containing gas into the chamber; and (c) a step of removing the metal fluoride layer by supplying a second processing gas containing a chlorine-containing gas into the chamber.

2. The dry development method according to claim 1, wherein the metal-containing resist contains at least one selected from the group consisting of tin, hafnium, and titanium.

3. The dry development method according to claim 1 or 2, wherein the metal-containing resist is an EUV resist.

4. The dry development method according to claim 1 or 2, wherein in the step (b), the metal fluoride layer is formed without generating plasma.

5. The dry development method according to claim 4, wherein the fluorine-containing gas contains at least one selected from the group consisting of hydrogen fluoride gas and xenon fluoride gas.

6. The dry development method according to claim 1 or 2, wherein in the step (b), the metal fluoride layer is formed using plasma generated from the fluorine-containing gas.

7. The dry development method according to claim 6, wherein the fluorine-containing gas contains at least one selected from the group consisting of hydrogen fluoride gas, xenon fluoride gas, nitrogen fluoride gas, fluorocarbon gas, hydrofluorocarbon gas, and sulfur fluoride gas.

8. The dry development method according to claim 1 or 2, wherein in the step (b), the temperature of the substrate support portion is 30 °C or higher.

9. The dry development method according to claim 1 or 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.

10. The dry development method according to claim 1 or 2, wherein in the step (c), the temperature of the substrate support portion is 30 °C or higher.

11. The dry development method according to claim 1 or 2, further comprising: (d) repeatedly performing the steps (b) and (c).

12. The dry development method according to claim 11, wherein the step (d) includes the following steps: changing at least one selected from the group consisting of the pressure in the chamber, the temperature of the substrate support portion, the processing time of the step (b), and the processing time of the step (c) according to the aspect ratio of the recess formed in the metal-containing resist in the step (c).

13. The dry development method according to claim 11, wherein the step (d) includes the following steps: performing at least one of reducing the pressure in the chamber, reducing the temperature of the substrate support portion, shortening the processing time of the step (b), and shortening the processing time of the step (c) according to an increase in the aspect ratio of the recess formed in the metal-containing resist in the step (c).

14. The dry development method according to claim 11, wherein, the step (d) includes: a first period during which the step (b) is performed for a first processing time and the step (c) is performed for a second processing time; and a second period after the first period during which the step (b) is performed for a third processing time shorter than the first processing time and the step (c) is performed for a fourth processing time shorter than the second processing time.

15. The dry development method according to claim 11, wherein, in the step (d), one of the first processing gas and the second processing gas is continuously supplied into the chamber, and the other of the first processing gas and the second processing gas is supplied into the chamber in such a manner that a first gas flow rate and a second gas flow rate smaller than the first gas flow rate are alternated.

16. The dry development method according to claim 1 or 2, wherein, the step (b) includes: a step of forming the metal fluoride layer without generating plasma; and a step of generating plasma from the first processing gas to form the metal fluoride layer.

17. The dry development method according to claim 1 or 2, wherein, at least one of after the step (b) and after the step (c) includes a step of purifying the internal space of the chamber.

18. The dry development method according to claim 1 or 2, wherein, in each cycle including the step (b) and the step (c), the thickness of the second region removed in the direction from the metal-containing resist toward the base film is 5 nm or more and 20 nm or less.

19. The dry development method according to claim 1 or 2, wherein, the partial pressure of the chlorine-containing gas is 13.3 Pa or more and 13.3 kPa or less.

20. The dry development method according to claim 1 or 2, wherein, the step (b) is performed at a first temperature, and the step (c) is performed at a second temperature higher than the first temperature.

21. A dry development method, comprising: (a) a step of providing a substrate on a substrate support portion in a chamber, wherein the substrate includes a base film and a metal-containing resist on the base film, and the metal-containing resist has an exposed first region and an unexposed second region; and (b) a step of removing the second region by supplying a processing gas containing a fluorine-containing gas and a chlorine-containing gas into the chamber.

22. The dry development method according to claim 21, wherein, the step (b) includes the following steps: reducing the pressure in the chamber according to an increase in the aspect ratio of the recess formed in the metal-containing resist.

23. A dry development apparatus, comprising: a chamber; a substrate support portion for supporting a substrate in the chamber, the substrate including a base film and a metal-containing resist on the base film, and the metal-containing resist having an exposed first region and an unexposed second region; a gas supply portion configured to supply a first processing gas containing a fluorine-containing gas and a second processing gas containing a chlorine-containing gas into the chamber; and a control portion, the control portion being configured to, By supplying the first processing gas into the chamber, a metal fluoride layer is formed on the surface of the second region. By supplying the second processing gas into the chamber, the metal fluoride layer is removed, and the gas supply unit is controlled.

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