Development method and development device

Abstract

A development method according to the present invention comprises: (a) a step for providing a substrate on a substrate support part inside a chamber, the substrate including a base film and a metal-containing layer on the base film, the metal-containing layer having a first region that is exposed, a second region that is not exposed, and a third region located between the first region and the second region, and the third region including a first portion adjacent to the first region and a second portion adjacent to the first portion; (b) a step for supplying energy to the substrate so as to modify at least one portion, of the second portion, adjacent to the first portion; (c) a step for supplying a first processing gas into the chamber so as to, in contrast to the first region, the first portion, and the at least one modified portion, selectively remove the second region; and (d) a step for, after (c), supplying a second processing gas into the chamber so as to remove the at least one portion.

Description

Development Method and Development Apparatus

[0001] Exemplary embodiments of the present disclosure relate to a development method and a development apparatus.

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

[0003] Japanese Patent Translation Publication No. 2021-523403

[0004] The present disclosure provides a development method and a development apparatus capable of reducing the exposure amount for obtaining a desired dimension.

[0005] In one exemplary embodiment, the development method includes: (a) a step of providing a substrate on a substrate support portion in a chamber, the substrate including an underlayer film and a metal-containing layer on the underlayer film, the metal-containing layer having an exposed first region, an unexposed second region, and a third region located between the first region and the second region, the third region including a first portion adjacent to the first region and a second portion adjacent to the first portion; (b) a step of supplying energy to the substrate to modify at least a part of the second portion adjacent to the first portion; (c) a step of supplying a first processing gas into the chamber to selectively remove the second region with respect to the first region, the first portion, and the at least a part of the modified second portion; and (d) a step of supplying a second processing gas into the chamber to remove the at least a part of the modified second portion after (c).

[0006] According to one exemplary embodiment, a development method and a development apparatus capable of reducing the exposure amount for obtaining a desired dimension are provided.

[0007] FIG. 1 is a diagram for explaining a configuration example of a heat treatment system. FIG. 2 is a diagram for explaining a configuration example of a plasma treatment system. FIG. 3 is a diagram for explaining a configuration example of a capacitively coupled plasma processing apparatus. FIG. 4 is a block diagram for explaining a configuration example of a substrate processing system according to one exemplary embodiment. FIG. 5 is a flowchart of a development method according to one exemplary embodiment. FIG. 6 is a partially enlarged view of a substrate in an example to which the development method of FIG. 5 can be applied. FIG. 7 is a cross-sectional view showing a step of a development method according to one exemplary implementation. FIG. 8 is a cross-sectional view showing a step of a development method according to one exemplary implementation. FIG. 9 is a cross-sectional view showing a step of a development method according to one exemplary implementation. FIG. 10 is a cross-sectional view showing a step of a development method according to one exemplary implementation. FIG. 11 is a flowchart of a development method according to one exemplary embodiment. FIG. 12 is a graph showing an example of the relationship between CD and exposure dose in the first to third experiments. FIG. 13 is a graph showing an example of the relationship between LWR and exposure dose in the first to third experiments. FIG. 14 is a graph showing an example of the relationship between CD and exposure dose in the fourth to sixth experiments.

[0008] Hereinafter, various exemplary embodiments will be described in detail with reference to the drawings. In each drawing, the same or corresponding parts will be denoted by the same reference numerals.

[0009] <Configuration Example of Heat Treatment System> FIG. 1 is a diagram for explaining a configuration example of a heat treatment system. In one embodiment, the heat treatment system includes a heat treatment apparatus 100 and a control unit 200. The heat treatment system is an example of a substrate processing system, and the heat treatment apparatus 100 is an example of a substrate processing apparatus. The heat treatment system is an example of a developing apparatus. That is, it can also be said that FIG. 1 is a diagram for explaining a configuration example of a developing apparatus according to one exemplary embodiment.

[0010] The heat treatment apparatus 100 has a processing chamber 102 configured to be sealed. The processing chamber 102 is, for example, an airtight cylindrical container and is configured to be able to adjust the internal atmosphere. A side wall heater 104 is provided on the side wall of the processing chamber 102. A ceiling heater 130 is provided on the ceiling wall (top plate) of the processing chamber 102. The ceiling surface 140 of the ceiling wall (top plate) of the processing chamber 102 is formed as a horizontal flat surface, and its temperature is adjusted by the ceiling heater 130.

[0011] A substrate support portion 121 is provided on the lower side inside the processing chamber 102. The substrate support portion 121 has a substrate support surface that supports the substrate W thereon. The substrate support portion 121 is, for example, formed in a circular shape in plan view, and the substrate W is placed on its horizontally formed surface (upper surface). A stage heater 120 is embedded in the substrate support portion 121. This stage heater 120 can heat the substrate W placed on the substrate support portion 121. In one embodiment, a heating device such as the stage heater 120 may function as an energy supply unit that supplies energy to the substrate W. Alternatively, instead of the heating device, a light irradiation device that irradiates light onto the substrate W may function as an energy supply unit that supplies energy to the substrate W. Note that a ring assembly (not shown) may be arranged around the substrate W on the substrate support portion 121. The ring assembly may include one or more annular members. By arranging the ring assembly around the substrate W, the temperature controllability of the outer peripheral region of the substrate W can be improved. The ring assembly may be composed of an inorganic material or an organic material according to the intended heat treatment.

[0012] The substrate support portion 121 is supported within the processing chamber 102 by columns 122 provided on the bottom surface of the processing chamber 102. On the outer side in the circumferential direction of the columns 122, a plurality of lift pins 123 that can move vertically are provided. Each of the plurality of lift pins 123 is inserted into a through-hole provided in the substrate support portion 121. The plurality of lift pins 123 are arranged at intervals in the circumferential direction. The lifting and lowering operations of the plurality of lift pins 123 are brought about by a lifting mechanism 124. When the lift pins 123 protrude from the surface of the substrate support portion 121, the transfer of the substrate W between a transfer mechanism (not shown) and the substrate support portion 121 becomes possible.

[0013] 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, and the like, and adjusts the exhaust flow rate from the exhaust port 131. By adjusting the exhaust flow rate and the like by this exhaust mechanism 132, the pressure inside the processing chamber 102 is adjusted. Note that on the side wall of the processing chamber 102, an opening / closing transfer port for the substrate W (not shown) is formed at a position different from the position where the exhaust port 131 opens.

[0014] 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. The gas nozzle 141 is provided on the side wall of the processing chamber 102 on the opposite side of the exhaust port 131 when viewed from the central portion of the substrate support portion 121. That is, the gas nozzle 141 is provided symmetrically with the exhaust port 131 with respect to a vertical virtual plane passing through the central portion of the substrate support portion 121 on the side wall of the processing chamber 102.

[0015] The gas nozzle 141 is formed in a rod shape that protrudes from the side wall of the processing chamber 102 toward the center side of the processing chamber 102. The tip of the gas nozzle 141 extends horizontally, for example, from the side wall of the processing chamber 102. The processing gas is discharged into the processing chamber 102 from the discharge port that opens at the tip of the gas nozzle 141, flows in the direction of the dashed-dotted arrow shown in FIG. 1, and is exhausted from the exhaust port 131. Note that the tip of the gas nozzle 41 may have a shape that extends obliquely downward toward the substrate W, or may have a shape that extends obliquely upward toward the ceiling surface 140 of the processing chamber 102.

[0016] The gas nozzle 141 may be provided, for example, on the ceiling wall of the processing chamber 102. Also, the exhaust port 131 may be provided on the bottom surface of the processing chamber 102.

[0017] The heat treatment apparatus 100 has a gas supply pipe 152 connected to the gas nozzle 141 from the outside of the processing chamber 102. A pipe heater 160 for heating the gas in the gas supply pipe 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 material in a liquid state.

[0018] The control unit 200 processes computer-executable instructions that cause the heat treatment apparatus 100 to execute various processes described in the present disclosure. The control unit 200 may be configured to control each element of the heat treatment apparatus 100 to execute the various processes described herein. In one embodiment, part or all of the control unit 200 may be included in the heat treatment apparatus 100. The control unit 200 may include a processing unit 200a1, a storage unit 200a2, and a communication interface 200a3. The control unit 200 is realized by, for example, a computer 200a. The processing unit 200a1 may be configured to perform various control operations by reading a program from the storage unit 200a2 and executing the read program. This program may be stored in the storage unit 200a2 in advance, or may be acquired via a medium when necessary. The acquired program is stored in the storage unit 200a2 and read from the storage unit 200a2 by the processing unit 200a1 and executed. 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 (Read Only Memory), an HDD (Hard Disk Drive), an SSD (Solid State Drive), or a combination thereof. The communication interface 200a3 may communicate with the heat treatment apparatus 100 via a communication line such as a LAN (Local Area Network).

[0019] <Configuration Example of Plasma Processing System> Fig. 2 is a diagram for explaining a configuration example when a plasma processing system is used as a development processing system. In one embodiment, the plasma processing system includes a plasma processing apparatus 1 and a control unit 2. The plasma processing system is an example of a developing apparatus. The plasma processing apparatus 1 includes a plasma processing chamber (hereinafter, also 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.

[0020] 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 excited plasma (HWP), surface wave plasma (SWP), or the like. 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 within the range of 100 kHz to 10 GHz. Accordingly, the AC signal includes RF (Radio Frequency) signals and microwave signals. In one embodiment, the RF signal has a frequency within the range of 100 kHz to 150 MHz. Instead of or in addition to being configured to generate plasma within the plasma processing space, the plasma generation unit may be configured to supply plasma generated outside the plasma processing chamber into the plasma processing chamber. Such a configuration can generate plasma outside the plasma processing chamber and supply the generated plasma into the plasma processing space through a plasma supply port disposed in the plasma processing chamber.

[0021] The control unit 2 processes computer-executable instructions that cause the plasma processing apparatus 1 to execute various processes described in the present disclosure. The control unit 2 may be configured to control each element of the plasma processing apparatus 1 to 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 is realized 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 configuration of the control unit 2 may be the same as each configuration of the control unit 200 (see FIG. 1) described above.

[0022] Next, a configuration example of a capacitively coupled plasma processing apparatus as an example of the plasma processing apparatus 1 will be described. FIG. 3 is a diagram for explaining a configuration example of a capacitively coupled plasma processing apparatus.

[0023] The capacitively coupled plasma processing apparatus 1 includes a plasma processing chamber 10, a gas supply unit 20, a power source 30, and an exhaust system 40. The plasma processing apparatus 1 also includes a substrate support unit 11 and a gas introduction unit. The gas introduction unit is configured to introduce at least one processing gas into the plasma processing chamber 10. The gas introduction unit includes a shower head 13. The substrate support unit 11 is disposed in the plasma processing chamber 10. The shower head 13 is disposed above the substrate support unit 11. In one embodiment, the shower head 13 constitutes at least a part of the ceiling of the plasma processing chamber 10. The plasma processing chamber 10 has a plasma processing space 10s defined by the shower head 13, the side wall 10a of the plasma processing chamber 10, and the substrate support unit 11. The plasma processing chamber 10 is grounded. The shower head 13 and the substrate support unit 11 are electrically insulated from the housing of the plasma processing chamber 10.

[0024] The substrate support portion 11 includes a main body portion 111 and a ring assembly 112. The main body portion 111 has a central region 111a for supporting the substrate W and an annular region 111b for supporting the ring assembly 112. The wafer is an example of the substrate W. The annular region 111b of the main body portion 111 surrounds the central region 111a of the main body portion 111 in plan view. The substrate W is disposed on the central region 111a of the main body portion 111, and the ring assembly 112 is disposed on the annular region 111b of the main body portion 111 so as to surround the substrate W on the central region 111a of the main body portion 111. Therefore, the central region 111a is also referred to as a substrate support surface for supporting the substrate W, and the annular region 111b is also referred to as a ring support surface for supporting the ring assembly 112.

[0025] In one embodiment, the main body portion 111 includes a base 1110 and an electrostatic chuck 1111. The base 1110 includes a conductive member. The conductive member of the base 1110 can function as a lower electrode. The electrostatic chuck 1111 is disposed on the base 1110. The electrostatic chuck 1111 includes a ceramic member 1111a and an electrostatic electrode 1111b disposed within the ceramic member 1111a. The ceramic member 1111a has a central region 111a. In one embodiment, the ceramic member 1111a also has an annular region 111b. Note that other members surrounding the electrostatic chuck 1111, such as an annular electrostatic chuck or an annular insulating member, may have the annular region 111b. In this case, the ring assembly 112 may be disposed on the annular electrostatic chuck or the annular insulating member, or may be disposed on both the electrostatic chuck 1111 and the annular insulating member. Also, at least one RF / DC electrode coupled to an RF power supply 31 and / or a DC power supply 32 described later may be disposed within the ceramic member 1111a. In this case, the at least one RF / DC electrode functions as a lower electrode. When a bias RF signal and / or a DC signal described later is supplied to the at least one RF / DC electrode, the RF / DC electrode is also referred to as a bias electrode. Note that the conductive member of the base 1110 and the at least one RF / DC electrode may function as a plurality of lower electrodes. Also, the electrostatic electrode 1111b may function as a lower electrode. Therefore, the substrate support portion 11 includes at least one lower electrode.

[0026] The ring assembly 112 includes one or more annular members. In one embodiment, the one or more annular members include one or more edge rings and at least one 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.

[0027] Further, the substrate support portion 11 may include a temperature control module configured to adjust at least one of the electrostatic chuck 1111, the ring assembly 112, and the substrate to a target temperature. The temperature control module may include a heater, a heat transfer medium, a flow path 1110a, or a combination thereof. A heat transfer fluid such as brine or gas flows through the flow path 1110a. In one embodiment, the flow path 1110a is formed in the base 1110, and one or more heaters are disposed in the ceramic member 1111a of the electrostatic chuck 1111. Further, the substrate support portion 11 may include a heat transfer gas supply portion configured to supply a heat transfer gas to a gap between the back surface of the substrate W and the central region 111a.

[0028] The shower head 13 is configured to introduce at least one process gas from the gas supply portion 20 into the plasma processing space 10s. The shower head 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 process gas supplied to the gas supply port 13a passes through the gas diffusion chamber 13b and is introduced into the plasma processing space 10s from the plurality of gas introduction ports 13c. Further, the shower head 13 includes at least one upper electrode. The gas introduction portion may include, in addition to the shower head 13, one or more side gas injection portions (SGI: Side Gas Injector) attached to one or more openings formed in the side wall la.

[0029] The gas supply unit 20 may include at least one gas source 21 and at least one flow controller 22. In one embodiment, the gas supply unit 20 is configured to supply at least one processing gas from the corresponding gas source 21 to the shower head 13 via the corresponding flow controller 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 for modulating or pulsing the flow rate of at least one processing gas.

[0030] 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, plasma is formed from at least one processing gas supplied to the plasma processing space 10s. Therefore, the RF power supply 31 can function as at least a part of the plasma generation unit 12. Also, by supplying a bias RF signal to at least one lower electrode, a bias potential is generated on the substrate W, and the ion component in the formed plasma can be drawn into the substrate W.

[0031] In one embodiment, the RF power supply 31 includes a first RF generation unit 31a and a second RF generation unit 31b. The first RF generation unit 31a is coupled to at least one lower electrode and / or at least one upper electrode via at least one impedance matching circuit, and is configured to generate a source RF signal (source RF power) for plasma generation. In one embodiment, the source RF signal has a frequency within 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.

[0032] The second RF generation unit 31b is coupled to at least one lower electrode via at least one impedance matching circuit and is configured to generate a bias RF signal (bias RF power). The frequency of the bias RF signal may be the same as or different from the frequency of the source RF signal. In one embodiment, the bias RF signal has a frequency lower than the frequency of the source RF signal. In one embodiment, the bias RF signal has a frequency within the range of 100 kHz to 60 MHz. In one embodiment, the second RF generation unit 31b may be configured to generate a plurality of bias RF signals having different frequencies. The generated one or more bias RF signals are supplied to at least one lower electrode. Also, in various embodiments, at least one of the source RF signal and the bias RF signal may be pulsed.

[0033] Also, the power supply 30 may include a DC power supply 32 coupled to the plasma processing chamber 10. The DC power supply 32 includes a first DC generation unit 32a and a second DC generation unit 32b. In one embodiment, the first DC generation unit 32a is connected to at least one lower electrode and is configured to generate a first DC signal. The generated first DC signal is applied to at least one lower electrode. In one embodiment, the second DC generation unit 32b is connected to at least one upper electrode and is configured to generate a second DC signal. The generated second DC signal is applied to at least one upper electrode.

[0034] In various embodiments, the first and second DC signals may be pulsed. In this case, a sequence of voltage pulses is applied to at least one lower electrode and / or at least one upper electrode. The voltage pulses may have a pulse waveform that is 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. Accordingly, the first DC generation unit 32a and the waveform generation unit constitute a voltage pulse generation unit. When the second DC generation unit 32b and the waveform generation unit constitute a voltage pulse generation unit, the voltage pulse generation unit is connected to at least one upper electrode. The voltage pulses may have a positive polarity or a negative polarity. Also, the sequence of voltage pulses may include one or more positive-polarity voltage pulses and one or more negative-polarity voltage pulses within one cycle. Note that the first and second DC generation units 32a and 32b may be provided in addition to the RF power supply 31, or the first DC generation unit 32a may be provided in place of the second RF generation unit 31b.

[0035] The exhaust system 40 can be connected to, for example, a gas discharge port 10e provided at the bottom of the plasma processing chamber 10. The exhaust system 40 may include a pressure regulating valve and a vacuum pump. The pressure in the plasma processing space 10s is adjusted by the pressure regulating valve. The vacuum pump may include a turbo molecular pump, a dry pump, or a combination thereof.

[0036] <Configuration Example of Substrate Processing System> FIG. 4 is a block diagram for explaining a configuration example of a substrate processing system SS according to an exemplary embodiment. The substrate processing system SS includes a first carrier station CS1, a first processing station PS1, a first interface station IS1, and an exposure apparatus EX. The substrate processing system SS further includes a second interface station IS2, a second processing station PS2, a second carrier station CS2, and a control unit CT. In one embodiment, in the substrate processing system SS, the second processing station PS2 functions as a developing apparatus. That is, the second processing station PS2 is an example of a developing apparatus. In another embodiment, a plasma processing apparatus 1 disposed downstream of the second carrier station CS2 may function as a developing apparatus together with the second carrier station CS2.

[0037] The first carrier station CS1 carries in and out the first carrier C1 between the first carrier station CS1 and a system external to the substrate processing system SS. The first carrier station CS1 has a mounting table including a plurality of first mounting plates ST1. On each first mounting plate ST1, the first carrier C1 in a state of accommodating a plurality of substrates W or in an empty state is mounted. The first carrier C1 has a housing capable of accommodating a plurality of substrates W therein. The first carrier C1 is, for example, a FOUP (Front Opening Unified Pod).

[0038] Further, the first carrier station CS1 transports the substrate W between the first carrier C1 and the first processing station PS1. The first carrier station CS1 further includes a first transfer device HD1. The first transfer device HD1 is provided in the first carrier station CS1 so as to be positioned between the mounting table and the first processing station PS1. The first transfer device HD1 transfers and delivers the substrate W between the first carrier C1 on each first mounting plate ST1 and the second transfer device HD2 of the first processing station PS1. The substrate processing system SS may further include a load lock module. The load lock module may be provided between the first carrier station CS1 and the first processing station PS1. The load lock module can switch the pressure inside thereof between atmospheric pressure and vacuum. "Atmospheric pressure" may be the pressure inside the first transfer device HD1. "Vacuum" is a pressure lower than atmospheric pressure and may be, 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 may transfer the substrate W, for example, from the first transfer device HD1 at atmospheric pressure to the second transfer device HD2 at vacuum, and also transfer the substrate W from the second transfer device HD2 at vacuum to the first transfer device HD1 at atmospheric pressure.

[0039] The first processing station PS1 performs various processes on the substrate W. In one embodiment, the first processing station PS1 includes a preprocessing module PM1, a resist film forming module PM2, and a first heat treatment module PM3 (hereinafter also collectively referred to as "the first substrate processing module"). Further, the first processing station PS1 has a second transfer device HD2 for transporting the substrate W. The second transfer device HD2 transfers and delivers the substrate W between two designated first substrate processing modules, and between the first processing station PS1 and the first carrier station CS1 or the first interface station IS1.

[0040] In the pretreatment module PM1, pretreatment is performed on the substrate W. In one embodiment, the pretreatment module PM1 includes a temperature adjustment unit for adjusting the temperature of the substrate W, a high-precision temperature control unit for precisely adjusting the temperature of the substrate W, and the like. In one embodiment, the pretreatment module PM1 includes a surface modification treatment unit for performing a surface modification treatment on the substrate W. Each processing unit of the pretreatment module PM1 may be configured to include a heat treatment apparatus 100 (see FIG. 1) and a plasma processing apparatus 1 (see FIGS. 2 and 3).

[0041] In the resist film forming module PM2, a resist film is formed on the substrate W. In one embodiment, the resist film forming module PM2 includes a dry coating unit. The dry coating unit forms a resist film on the substrate W using a dry process such as a vapor deposition method. The dry coating unit, for example, includes a CVD apparatus or an ALD apparatus for chemically vapor-depositing a resist film or a PVD apparatus for physically vapor-depositing a resist film on the substrate W disposed in the chamber. The dry coating unit may be a heat treatment apparatus 100 (see FIG. 1) or a plasma processing apparatus 1 (see FIGS. 2 and 3).

[0042] In one embodiment, the resist film forming module PM2 includes a wet coating unit. The wet coating unit forms a resist film on the substrate W using a wet process such as a liquid deposition method. The wet coating unit may be, for example, a liquid processing apparatus.

[0043] In one embodiment, an example of the resist film forming module PM2 includes both a wet coating unit and a dry coating unit.

[0044] In the first heat treatment module PM3, a substrate W is subjected to heat treatment. In one embodiment, the first heat treatment module PM3 includes any one or more of a pre-bake (PAB) unit that performs heat treatment on the substrate W on which a resist film is formed, a temperature adjustment unit that adjusts the temperature of the substrate W, and a high-precision temperature control unit that adjusts the temperature of the substrate W with high precision. Each of these units may have one or more heat treatment apparatuses. In one example, the plurality of heat treatment apparatuses may be stacked. The heat treatment apparatus may be, for example, the heat treatment apparatus 100 (see FIG. 1). Each heat treatment may be performed using a predetermined gas at a predetermined temperature.

[0045] The first interface station IS1 has a third transfer device HD3. The third transfer device HD3 transfers and delivers the substrate W between the first processing station PS1 and the exposure apparatus EX. The third transfer device HD3 has a housing that houses the substrate W, and the temperature, humidity, pressure, etc. inside the housing may be configured to be controllable.

[0046] The exposure apparatus EX exposes the resist film on the substrate W using an exposure mask (reticle). The exposure apparatus EX may be, for example, an EUV exposure apparatus having a light source that generates EUV light.

[0047] The second interface station IS2 has a fourth transfer device HD4. The fourth transfer device HD4 transfers and delivers the substrate W between the exposure apparatus EX and the second processing station PS2. The fourth transfer device HD4 has a housing that houses the substrate W, and the temperature, humidity, pressure, etc. inside the housing may be configured to be controllable.

[0048] 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 also collectively referred to as the "second substrate processing module"). The second processing station PS2 also has a fifth transfer device HD5 for transferring the substrate W. The fifth transfer device HD5 transfers and delivers the substrate W between two designated second substrate processing modules, and between the second processing station PS2 and the second carrier station CS2 or the second interface station IS2.

[0049] In the second heat treatment module PM4, the substrate W is heat-treated. The second heat treatment module PM4 may include any one or more of a post-exposure bake (PEB) unit for performing a heat treatment on the exposed substrate W, a temperature adjustment unit for adjusting the temperature of the substrate W, and a high-precision temperature control unit for adjusting the temperature of the substrate W with high precision. Each of these units may have one or more heat treatment apparatuses. In one example, the plurality of heat treatment apparatuses may be stacked. The heat treatment apparatus may be, for example, the heat treatment apparatus 100 (see FIG. 1). Each heat treatment may be performed using a predetermined gas at a predetermined temperature.

[0050] In the measurement module PM5, various measurements are performed on the substrate W. In one embodiment, the measurement module PM5 includes an imaging unit that includes a stage on which the substrate W is placed, an imaging device, a lighting device, and various sensors (such as a temperature sensor, a reflectance measurement sensor, etc.). The imaging device may be, for example, a CCD camera that images the appearance of the substrate W. Alternatively, the imaging device may be a hyperspectral camera that spectrally separates light for each wavelength and takes a photograph. The hyperspectral camera can measure any one or more of the pattern shape, dimensions, film thickness, composition, and film density of the resist film.

[0051] In the development module PM6, a development process is performed on the substrate W. In one embodiment, the development module PM6 includes a dry development unit that performs dry development on the substrate W. The dry development unit may be, for example, a heat treatment apparatus 100 (see FIG. 1) or a plasma treatment apparatus 1 (see FIGS. 2 and 3).

[0052] In the third heat treatment module PM7, a heat treatment is performed on the substrate W. The third heat treatment module PM7 may include any one or more of a post-bake (PB) unit that performs a heat treatment on the developed substrate W, a temperature adjustment unit that adjusts the temperature of the substrate W, and a high-precision temperature control unit that adjusts the temperature of the substrate W with high precision. Each of these units may have one or more heat treatment apparatuses. In one example, the plurality of heat treatment apparatuses may be stacked. The heat treatment apparatus may be, for example, the heat treatment apparatus 100 (see FIG. 1). Each heat treatment may be performed using a predetermined gas at a predetermined temperature.

[0053] The second carrier station CS2 carries in and out the second carrier C2 between the second carrier station CS2 and a system outside the substrate processing system SS. The configuration and function of the second carrier station CS2 may be the same as those of the first carrier station CS1 described above.

[0054] The control unit CT controls each component of the substrate processing system SS to execute a given process on the substrate W. The control unit CT stores a recipe in which process procedures, process conditions, transfer conditions, etc. are set, and controls each component of the substrate processing system SS to execute a given process on the substrate W according to the recipe. In one embodiment, part or all of the control unit CT may be included in the substrate processing system SS. The control unit CT may兼 have part or all of the functions of each control unit (the control units 200 and 2 shown in FIGS. 1 to 3).

[0055] It should be noted that the term "兼" in the translation of is used to represent the idea of "also having" or "combining" in the original text, but it may need to be adjusted according to the specific context to make the translation more accurate and fluent.FIG. 5 is a flowchart of a development method according to one exemplary embodiment. The development method shown in FIG. 5 (hereinafter referred to as "method MT1") can be executed by the developing apparatus of the above embodiment. Method MT1 can be applied to substrate W. Method MT1 may include steps ST11 to ST19. Steps ST11 to ST19 can be executed in order. Method MT1 may not include at least one of steps ST13, ST15, ST16, ST17, and ST19. Method MT1 may be executed using the second processing station PS2 of the substrate processing system SS shown in FIG. 4. In method MT1, in the second processing station PS2, the dry development unit included in the development module PM6 is, for example, the heat treatment apparatus 100. A plasma processing apparatus 1 is arranged, for example, downstream of the second carrier station CS2. Hereinafter, referring to FIGS. 6 to 10, a case where the control unit CT controls each part of the substrate processing system SS and the plasma processing apparatus 1 to execute method MT1 on the substrate W will be described as an example.

[0056] FIG. 6 is a cross-sectional view of a substrate in an example to which the method of FIG. 5 can be applied. As shown in FIG. 6, the substrate W includes a base region UR and a metal-containing layer ML on the base region UR. Substrate W may be used in the manufacture of semiconductor devices. Semiconductor devices include, for example, memory devices such as DRAM and 3D-NAND flash memories and logic devices.

[0057] The base region UR may be formed on a silicon wafer. The base region UR may be a carbon-containing film, a dielectric film, a metal film, a semiconductor film, or a laminated film thereof.

[0058] The metal-containing layer ML may be a resist film containing a metal. The metal may include at least one metal selected from the group consisting of tin (Sn), hafnium (Hf), and titanium (Ti). The metal-containing layer ML may include a metal oxide. In one example, the metal-containing layer ML contains tin and may include tin oxide (Sn—O bond) or tin hydroxide (Sn—OH bond).

[0059] As shown in FIG. 6, the metal-containing layer ML has an exposed first region R1, an unexposed second region R2, and a third region R3 located between the first region R1 and the second region R2. The first region R1 may be an exposure region exposed by EUV. The first region R1 may have a line pattern, or may have a hole pattern and a pillar pattern. The second region R2 may be an unexposed region not exposed by EUV. "Unexposed" means that the exposure amount is below a threshold value.

[0060] The ratio of the width of the third region R3 to the width of the first region R1 may be 5% or more, or may be 15% or more. The width of the first region R1 may be the CD (Critical Dimension) of the first region R1 on the upper surface of the metal-containing layer ML. The width of the third region R3 may be the length of the third region R3 on the upper surface of the metal-containing layer ML (the distance between the first region R1 and the second region R2).

[0061] The third region R3 may be an intermediate exposure region located between the first region R1 and the second region R2. That is, the third region R3 may be a region exposed by EUV. On the upper surface of the metal-containing layer ML, the exposure amount at the boundary between the second region R2 and the third region R3 may be 15% of the exposure amount (maximum exposure amount) at the center of the width of the first region R1. The exposure amount at the boundary between the first region R1 and the third region R3 may be 50% of the exposure amount (maximum exposure amount) at the center of the width of the first region R1. The exposure amount of the first region R1 may be greater than the exposure amount of the third region R3. The exposure amount of the third region R3 may be greater than the exposure amount of the second region R2. The exposure amount may continuously decrease from the first region R1 toward the second region R2.

[0062] The third region R3 includes a first portion R3a adjacent to the first region R1 and a second portion R3b adjacent to the first portion R3a. The second portion R3b may be adjacent to the second region R2. The second portion R3b may be located between the first portion R3a and the second region R2. The exposure amount of the first portion R3a may be greater than the exposure amount of the second portion R3b.

[0063] In one embodiment, the substrate W is formed as follows. First, as shown in FIG. 4, a first carrier C1 containing a plurality of substrates W is carried into the first carrier station CS1 of the substrate processing system SS. The first carrier C1 is placed on the first mounting plate ST1. Next, by the first transfer device HD1, each substrate W in the first carrier C1 is sequentially taken out and delivered to the second transfer device HD2 of the first processing station PS1. The substrate W is transferred to the preprocessing module PM1 by the second transfer device HD2. The preprocessing module PM1 performs preprocessing on the substrate W. As the preprocessing, one or more of temperature adjustment of the substrate W, formation of part or all of the underlying film of the substrate W, heat treatment of the substrate W, and high-precision temperature adjustment of the substrate W may be performed. As the preprocessing, a surface modification treatment of the substrate W may be performed.

[0064] Next, a resist film containing a metal is formed on the underlying film subjected to the adhesion improvement treatment and the like. At this time, the substrate W is transferred to the resist film forming module PM2 by the second transfer device HD2. The resist film forming module PM2 forms a resist film on the substrate W. The formation of the resist film may be performed by a dry process, may be performed by a wet process such as a solution coating method, or may be performed by both a dry process and a wet process. When the formation of the resist film is performed by a dry process, for example, the resist film is formed by vapor-depositing the resist film on the substrate W using the dry coating unit of the resist film forming module PM2. When the formation of the resist film is performed by a wet process, for example, the resist film is formed by spin-coating the resist film on the substrate W using the wet coating unit of the resist film forming module PM2. When the formation of the resist film is performed by both a dry process and a wet process, for example, a first resist film may be formed on the substrate W by a dry process and then a second resist film may be formed on the first resist film by a wet process. In this case, the film thickness, material, and / or composition of the first resist film and the second resist film may be the same or different.

[0065] After the formation of the resist film, the substrate W is subjected to a heat treatment, that is, a post - apply bake (PAB). At this time, the substrate W is transported to the first heat treatment module PM3 by the second transfer device HD2. The first heat treatment module PM3 performs a heat treatment (pre - bake: PAB) on the substrate W. The pre - bake may be performed in an air atmosphere or in an inert atmosphere. Also, the pre - bake may be performed by heating the substrate W to 50°C or higher and 250°C or lower, 50°C or higher and 200°C or lower, or 80°C or higher and 150°C or lower. When the formation of the resist film is performed by a dry process, in one embodiment, the pre - bake may be continuously performed by the dry coating that executed the dry process. In one embodiment, after the pre - bake, a process of removing the resist film at the edge of the substrate W (Edge Bead Removal: EBR) may be performed.

[0066] The resist film on the substrate W after the heat treatment (pre - bake) is irradiated with EUV light through an exposure mask (reticle). At this time, first, the substrate W is transferred from the second transfer device HD2 to the third transfer device HD3 of the first interface station IS1. Then the substrate W is transported to the exposure device EX by the third transfer device HD3. The substrate W undergoes EUV exposure through an exposure mask (reticle) in the exposure device EX. Thereby, a substrate W including a metal - containing layer ML including a base region UR, an exposed first region R1, an unexposed second region R2, and a third region R3 located between the first region R1 and the second region is formed. The first region R1 and the third region R3 are regions corresponding to the openings provided in the exposure mask (reticle). The second region R2 is a region corresponding to the pattern (non - opening region) that shields EUV light provided in the exposure mask (reticle). EUV has a wavelength in the range of, for example, 10 nm to 20 nm. EUV may have a wavelength in the range of 11 nm to 14 nm and, in one example, has a wavelength of 13.5 nm.

[0067] (Step ST11) In step ST11, the substrate W shown in FIG. 6 is provided on the substrate support portion in the chamber. In step ST11, first, the substrate W may be transferred from the fourth transfer device HD4 of the second interface station IS2 to the fifth transfer device HD5 of the second processing station PS2. Next, the substrate W may be transferred to the second heat treatment module PM4 by the fifth transfer device HD5. That is, step ST11 may be performed in the second heat treatment module PM4. As described above, the second heat treatment module PM4 includes any one or more of a PEB unit that performs heat treatment on the substrate W after exposure, 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. Each of these units may have, for example, one or more heat treatment apparatuses 100. Therefore, in step ST11, the substrate W transferred to the second heat treatment module PM4 can be provided on the substrate support portion 121 in the processing chamber 102 in the heat treatment apparatus 100 included in the second heat treatment module PM4. The substrate W can be supported by the substrate support portion 121 in the processing chamber 102.

[0068] (Step ST12) As shown in FIG. 7, in step ST12, energy is supplied to the substrate W to modify at least a part (for example, a part R3b1 of the second part R3b or the whole of the second part R3b) adjacent to the first part R3a in the second part R3b. Step ST12 may be performed in the second heat treatment module PM4, similar to step ST11.

[0069] Alternatively, step ST12 may be performed in the development module PM6. In this case, in step ST12, the substrate W may be transferred to the development module PM6 by the fifth transfer device HD5. Alternatively, step ST12 may be performed in the third heat treatment module PM7. In this case, the substrate W may be transferred to the third heat treatment module PM7 by the fifth transfer device HD5.

[0070] In step ST12, the substrate W may be heated as a means of supplying energy to the substrate W. In step ST12, the substrate W may be heated under two or more different conditions as a means of supplying energy to the substrate W. That is, step ST12 may include step ST12a and step ST12b. Step ST12a and step ST12b may be performed in the same chamber, or may be performed in different chambers from each other.

[0071] In step ST12a, for example, the substrate W is heated under the first condition. Step ST12a is, for example, a post-exposure bake (PEB).

[0072] The first heating time, which is the heating time under the first condition, may be 5 seconds or more. Alternatively, the first heating time may be 30 seconds or more. The first heating time may be 200 seconds or less. Alternatively, the first heating time may be 150 seconds or less.

[0073] The first heating temperature, which is the heating temperature under the first condition, may be 150°C or more. Alternatively, the first heating temperature may be 160°C or more, or may be 170°C or more. The first heating temperature may be 250°C or less. Alternatively, the first heating temperature may be 240°C or less, or may be 230°C or less.

[0074] In step ST12b, for example, the substrate W is heated under a second condition different from the first condition. Step ST12b is, for example, an additional heat treatment (Add Bake) after PEB.

[0075] The second heating time, which is the heating time under the second condition, may be longer than the first heating time. The second heating time may be 10 seconds or more. Alternatively, the second heating time may be 30 seconds or more. The second heating time may be 300 seconds or less. Alternatively, the second heating time may be 200 seconds or less.

[0076] The second heating temperature, which is the heating temperature under the second condition, may be higher than the first heating temperature. The second heating temperature may be 5°C or more higher than the first heating temperature, or may be 10°C or more higher. The second heating temperature may be 170°C or more. Alternatively, the second heating temperature may be 180°C or more, or may be 190°C or more. The second heating temperature may be 300°C or less. Alternatively, the second heating temperature may be 280°C or less.

[0077] In step ST12, the substrate W may not be heated under two or more different conditions. Step ST12 may not include step ST12a and step ST12b. In this case, in step ST12, the substrate W may be heated under a single condition.

[0078] The heating time under the single condition may be 60 seconds or more. Alternatively, the heating time under the single condition may be 90 seconds or more, or may be 120 seconds or more. The heating time under the single condition may be 600 seconds or less. Alternatively, the heating time under the single condition may be 300 seconds or less.

[0079] The heating temperature under the single condition may be 120°C or more. Alternatively, the heating temperature under the single condition may be 150°C or more, or may be 180°C or more. The heating temperature under the single condition may be 400°C or less. Alternatively, the heating temperature under the single condition may be 300°C or less.

[0080] In one embodiment, when the substrate W is heated under a single condition, in step ST12, the substrate W may be heated under the condition of 200°C or more and 60 seconds or more. In step ST12, the substrate W may be heated under reduced pressure or under vacuum.

[0081] In step ST12, the atmosphere when heating the substrate W may include air, H ２ O, CO ２ 、CO、O ２ 、O ３ 、inert gas, etc.

[0082] In step ST12, as energy is supplied to the substrate W, the substrate W may be irradiated with light. The light may be light from EUV to infrared. The wavelength of the light may be from 13 nm to 10 cm. The light may be UV or DUV. As energy is supplied to the substrate W, the substrate W may be exposed to plasma.

[0083] In method MT1, by heating the substrate W in step ST12, as shown in FIG. 7, a part R3b1 adjacent to the first part R3a in the second part R3b is modified. That is, in method MT1, at the end of step ST12, the second part R3b1 may include a modified part R3b1 and an unmodified remaining part R3b2. The part R3b1 may be adjacent to the remaining part R3b2.

[0084] (Step ST13) In step ST13, measurement on the substrate W is performed. In step ST13, the substrate W may be conveyed to the measurement module PM5 by the fifth conveyance device HD5. That is, step ST13 may be performed in the measurement module PM5. In step ST13, the substrate W can be measured by the measurement module PM5. The measurement may be an optical measurement or other measurement. In one embodiment, the measurement by the measurement module PM5 includes measurement of the appearance and / or dimensions of the substrate W using a CCD camera. In one embodiment, the measurement by the measurement module PM5 includes 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. In step ST13, the pattern shape, etc. may be measured by a sensor provided on the conveyance path of the substrate W.

[0085] In one embodiment, the control unit CT determines the presence or absence of exposure abnormalities of the substrate W based on at least one of the measured appearance, dimensions, pattern shape, etc. of the substrate W. In one embodiment, when it is determined in the control unit CT that there are exposure abnormalities, the substrate W may be reworked or discarded without performing subsequent steps. The rework of the substrate W may be performed by removing the metal-containing layer ML on the substrate W and forming a new metal-containing layer ML on the underlying region UR. Although the rework of the substrate W after step ST14 may involve damage to the substrate W, performing the rework in step ST13 can avoid or suppress damage to the substrate W.

[0086] (Step ST14) As shown in FIG. 8, in step ST14, a first processing gas is supplied into the chamber to selectively remove the second region R2 and the remaining portion R3b2 with respect to the first region R1, the first portion R3a, and a part R3b1. That is, in step ST14, a first processing gas is supplied into the chamber to remove the second region R2 and the remaining portion R3b2 while leaving the first region R1, the first portion R3a, and a part R3b1. It can also be said that in step ST14, a first processing gas is supplied into the chamber to develop the metal-containing layer ML while leaving the first region R1, the first portion R3a, and a part R3b1. Step ST14 may be performed by dry development. At the end of step ST14, the supply of the first processing gas may be stopped. In step ST14, the substrate W may be exposed to the plasma generated from the first processing gas, or the substrate W may be exposed to the first processing gas without generating plasma.

[0087] In step ST14, the substrate W may be conveyed to the development module PM6 by the fifth transfer device HD5. That is, step ST14 may be performed in the development module PM6. As described above, the development module PM6 includes a dry development unit that performs dry development on the substrate W, and the dry development unit may be, for example, the heat treatment apparatus 100 (see FIG. 1). When step ST14 is performed in the development module PM6, a first processing gas may be supplied into the processing chamber 102 of the heat treatment apparatus 100 to selectively remove the second region R2 and the remaining portion R3b2 from the first region R1, the first portion R3a, and a part R3b1.

[0088] Alternatively, step ST14 may be performed in the second heat treatment module PM4. In this case, in step ST14, the substrate W may be conveyed to the second heat treatment module PM4 by the fifth transfer device HD5. Alternatively, step ST14 may be performed in the third heat treatment module PM7. In this case, in step ST14, the substrate W may be conveyed to the third heat treatment module PM7 by the fifth transfer device HD5.

[0089] In step ST14, the rate at which the part R3b1 is removed is 0.5 nm / min or less. Alternatively, in step ST14, the rate at which the part R3b1 is removed may be 3 nm / min or less, or may be 5 nm / min or less.

[0090] The first processing gas may contain at least one selected from the group consisting of hydrogen halide, carboxylic acid, and Lewis acid. The hydrogen halide contained in the first processing gas may contain at least one selected from the group consisting of hydrogen bromide and hydrogen chloride. The carboxylic acid contained in the first processing gas may contain acetic acid. The Lewis acid contained in the first processing gas may contain boron trichloride. The first processing gas may contain at least one gas selected from the group consisting of hydrogen bromide gas, hydrogen chloride gas, acetic acid gas, and boron trichloride gas.

[0091] In step ST14, the pressure inside the processing chamber 102 may be 760 Torr or less. Alternatively, in step ST14, the pressure inside the processing chamber 102 may be 10 Torr or less, or may be 1 Torr or less. In step ST14, the pressure inside the processing chamber 102 may be 5 mTorr or more. Alternatively, in step ST14, the pressure inside the processing chamber 102 may be 10 mTorr or more, or may be 50 mTorr or more. 1 mTorr corresponds to 0.133322 Pa.

[0092] In step ST14, the temperature of the substrate support portion 121 may be 250 °C or less. Alternatively, in step ST14, the temperature of the substrate support portion 121 may be 200 °C or less, or may be 150 °C or less. In step ST14, the temperature of the substrate support portion 121 may be -30 °C or more. Alternatively, in step ST14, the temperature of the substrate support portion 121 may be 0 °C or more.

[0093] In one embodiment, in step ST14, while heating the substrate W at 60 °C to 200 °C, the substrate W is exposed to a first processing gas containing boron trichloride gas. In step ST14, as shown in FIG. 8, residue RD may occur. The residue RD may adhere to the surface of the underlying region UR. The residue RD may contain a metal contained in the metal-containing layer ML. That is, the residue RD may contain at least one metal selected from the group consisting of tin (Sn), hafnium (Hf), and titanium (Ti).

[0094] (Step ST15) In step ST15, the substrate W is heated. In step ST15, the substrate W may be transported to the third heat treatment module PM7 by the fifth transfer device HD5. That is, step ST15 may be performed in the third heat treatment module PM7. Step ST15 is, for example, a post bake. Step ST15 may be performed in an air atmosphere, or may be performed in a reduced pressure atmosphere containing nitrogen or oxygen. In step ST15, the heating temperature may be 150 °C or more, or may be 250 °C or less.

[0095] (Step ST16) In step ST16, measurement of the substrate W is performed. In step ST16, the substrate W may be conveyed to the measurement module PM5 by the fifth transfer device HD5. That is, step ST16 may be performed in the measurement module PM5, similar to step ST13. The measurement may be an optical measurement or other measurement. In step ST16 as well, the pattern shape or the like may be measured by a sensor provided on the conveyance path of the substrate W. The control unit CT may determine the presence or absence of abnormalities such as defects, scratches, and adhesion of foreign matter in the development pattern of the substrate W based on the appearance, dimensions, and / or pattern shape of the measured substrate W. If it is determined that there is an abnormality in the control unit CT, the substrate W may be reworked or discarded without performing the subsequent steps.

[0096] (Step ST17) As shown in FIG. 9, in step ST17, energy is supplied to the substrate W to modify the modified part R3b1 of the first region R1, the first part R3a, and the second part R3b. As a means of supplying energy to the substrate W, the substrate W may be exposed to plasma generated from an oxygen-containing gas. The oxygen-containing gas may contain O ２ gas. In one embodiment, in step ST17, the substrate W is exposed to plasma generated from an oxygen-containing gas.

[0097] In step ST17, the substrate W may be transferred by the fifth transfer device HD5 to the sixth transfer device HD6 of the second carrier station CS2 and then transferred by the sixth transfer device HD6 to the second carrier C2 of the second mounting plate ST2. Thereafter, the substrate W may be transferred together with the second carrier C2 to an external plasma processing apparatus 1 different from the second processing station PS2. The substrate W transferred to the plasma processing apparatus 1 may be provided in the plasma processing chamber 10. The substrate W may be supported by the substrate support portion 11 in the plasma processing chamber 10. That is, step ST17 may be performed in the plasma processing chamber 10 of the plasma processing apparatus 1.

[0098] Alternatively, in step ST17, as energy supply to the substrate W, the substrate W may be irradiated with light or heated. In this case, the substrate W may not be transferred to the above-described external plasma processing apparatus 1, and step ST17 may be performed in any one of the second heat treatment module PM4, the development module PM6, and the third heat treatment module PM7.

[0099] As shown in FIG. 9, at the end of step ST17, the metal-containing layer ML may include a modified first region R1A, a modified first portion R3aA, and a further modified part R3b1A. When the metal-containing layer ML is a resist film, the resist film can be cured by step ST17. Also, the adsorbed gas adsorbed on the inner wall of the plasma processing chamber 10 that houses the substrate W can be removed.

[0100] In step ST17, the pressure in the plasma processing chamber 10 may be 800 mTorr or less. Alternatively, in step ST17, the pressure in the plasma processing chamber 10 may be 500 mTorr or less, or may be 300 mTorr or less. In step ST17, the pressure in the plasma processing chamber 10 may be 3 mTorr or more. Alternatively, in step ST17, the pressure in the plasma processing chamber 10 may be 5 mTorr or more, or may be 10 mTorr or more.

[0101] In steps ST14 and ST17, the pressure in the processing chamber may be the same or different. That is, the pressure in the processing chamber 102 in step ST14 may be the same as or different from the pressure in the plasma processing chamber 10 in step ST17.

[0102] In step ST17, the temperature of the substrate support portion 11 may be 180° C. or less. Alternatively, in step ST17, the temperature of the substrate support portion 11 may be 120° C. or less, or may be 60° C. or less. In step ST17, the temperature of the substrate support portion 11 may be −30° C. or more. Alternatively, in step ST17, the temperature of the substrate support portion 11 may be 0° C. or more.

[0103] In steps ST14 and ST17, the temperature of the substrate support portion may be the same or different. That is, the temperature of the substrate support portion 121 in step ST14 may be the same as or different from the temperature of the substrate support portion 11 in step ST17.

[0104] (Step ST18) As shown in FIG. 10, in step ST18, a second processing gas is supplied into the chamber to remove a modified part R3b1A of the second portion R3b. Step ST18 may be performed in the plasma processing chamber 10 of the plasma processing apparatus 1, similarly to step ST17. Thus, in method MT1, steps ST11 to ST16 may be performed in the second processing station PS2, and steps ST17 and ST18 may be performed in the external plasma processing apparatus 1. That is, in method MT1, steps ST14 and ST18 may be performed in different chambers from each other. When the substrate W is irradiated with light or heated in step ST17, in step ST18, it may be transported to an external plasma processing apparatus 1 different from the second processing station PS2 through the above-described transport process.

[0105] In step ST18, the residue RD may be removed together with the part R3b1A. In step ST18, the part R3b1A and the residue RD may be removed from the modified first region R1A and the modified first portion R3a. As a result, the metal-containing layer ML may be formed into a desired dimension. For example, as shown in FIG. 10, the metal-containing layer ML may be formed such that the side surface of the first portion R3aA is perpendicular to the surface of the base region UR in a cross-sectional view of the substrate W. That is, in step ST18, the part R3b1A may be removed so that the shape of the side wall of the metal-containing layer ML becomes a vertical shape. At the end of step ST18, the supply of the second processing gas may be stopped.

[0106] The second processing gas may contain at least one selected from the group consisting of hydrogen halide, carboxylic acid, and Lewis acid. The second processing gas may further contain a carbon-containing gas. When the second processing gas contains a carbon-containing gas, a carbon-containing deposit is deposited on the upper surface of the metal-containing layer ML, so that the upper surface of the metal-containing layer ML can be protected. The second processing gas may further contain an inert gas. The hydrogen halide contained in the second processing gas may contain at least one selected from the group consisting of hydrogen bromide and hydrogen chloride. The carboxylic acid contained in the second processing gas may contain acetic acid. The Lewis acid contained in the second processing gas may contain boron trichloride. The carbon-containing gas contained in the second processing gas may contain a hydrocarbon gas such as methane gas. The inert gas contained in the second processing gas may contain nitrogen gas, argon gas, helium gas, etc. The second processing gas may contain at least one gas selected from the group consisting of hydrogen bromide gas, hydrogen chloride gas, acetic acid gas, and boron trichloride gas. The second processing gas may be the same as or different from the first processing gas.

[0107] In step ST18, the pressure in the plasma processing chamber 10 may be 800 mTorr or less. Alternatively, in step ST18, the pressure in the plasma processing chamber 10 may be 500 mTorr or less, or may be 300 mTorr or less. In step ST18, the pressure in the plasma processing chamber 10 may be 3 mTorr or more. Alternatively, in step ST18, the pressure in the plasma processing chamber 10 may be 5 mTorr or more.

[0108] In steps ST14 and ST18, the pressure in the processing chamber may be the same or different. That is, the pressure in the processing chamber 102 in step ST14 may be the same as or different from the pressure in the plasma processing chamber 10 in step ST18.

[0109] In step ST18, the temperature of the substrate support portion 11 may be 120°C or lower, or may be 80°C or lower. In step ST18, the temperature of the substrate support portion 11 may be -30°C or higher. Alternatively, in step ST18, the temperature of the substrate support portion 11 may be 0°C or higher.

[0110] In steps ST14 and ST18, the temperature of the substrate support portion may be the same or different. That is, the temperature of the substrate support portion 121 in step ST14 may be the same as or different from the temperature of the substrate support portion 11 in step ST18.

[0111] In step ST18, plasma may be generated from the second processing gas. In this case, the modified part R3b1 of the second part R3b may be removed using the plasma. Further, in step ST18, an electric bias may be applied to the substrate support portion 11, or the substrate W may be irradiated with a gas cluster ion beam. The gas cluster ion beam can be emitted from an ion beam generator. The emission direction of the gas cluster ion beam may be a direction perpendicular to the surface of the substrate W. Alternatively, in step ST18, while applying an electric bias to the substrate support portion .11, the second processing gas may be supplied into the plasma processing chamber 10, or while irradiating the substrate W with a gas cluster ion beam, the second processing gas may be supplied into the plasma processing chamber 10. In one embodiment, in step ST18, while applying an electric bias to the substrate support portion, the substrate W is exposed to plasma generated from a second processing gas containing hydrogen bromide gas, methane gas, and nitrogen gas.

[0112] (Step ST19) In step ST19, steps ST14 to ST18 are repeated. If at least one of steps ST15 to ST17 is not performed, in step ST19, the steps excluding the said step among steps ST14 to ST18 are repeated. That is, if step ST15 is not performed, in step ST19, steps ST14, step ST16, step ST17, and step ST18 are repeated. If step ST16 is not performed, in step ST19, steps ST14, step ST15, step ST17, and step ST18 are repeated. If step ST17 is not performed, in step ST19, steps ST14, step ST15, step ST16, and step ST18 are repeated.

[0113] According to the above-described developing apparatus and method MT1, in step ST14, the second region R2 and the remainder R3b2 are selectively removed with respect to the first region R1, the first portion R3a, and a part R3b1. Then, in step ST18, the modified part R3b1A of the second portion R3b is removed. By selectively removing the second region R2 and the remainder R3b2 as described above without removing the entire third region R3 in step ST14, the exposure amount for obtaining the desired dimension of the metal-containing layer ML can be reduced in step ST18. That is, according to the above-described developing apparatus and method MT1, the sensitivity can be improved. Further, according to the above-described developing apparatus and method MT1, the exposure amount described above can be reduced while reducing the roughness of the developed metal-containing layer ML, for example, LWR (Line Width Roughness).

[0114] In method MT1, in step ST12, energy may be supplied to the substrate W to modify the entire second portion R3b. Hereinafter, the differences from the above-described embodiment in the steps after step ST13 when the entire second portion R3b is modified in step ST12 will be mainly described.

[0115] At the end of step ST12, the second portion R3b1 may not include the unmodified remainder R3b2. In step ST14, a first processing gas may be supplied into the chamber to selectively remove the second region R2 from the entire first region R1, the first portion R3a, and the second portion R3b. That is, in step ST14, a first processing gas may be supplied into the chamber to remove the second region R2 while leaving the entire first region R1, the first portion R3a, and the second portion R3b intact.

[0116] In step ST17, energy may be supplied to the substrate W to modify the entire first region R1, the first portion R3a, and the modified second portion R3b. At the end of step ST17, the metal-containing layer ML may include a modified first region R1A, a modified first portion R3aA, and a further modified second portion R3b. In step ST18, a second processing gas may be supplied into the chamber to remove the entire modified second portion R3b. In step ST18, the residue RD may be removed together with the entire second portion R3b. In this case, in step ST18, the entire second portion R3b and the residue RD may be removed from the modified first region R1A and the modified first portion R3a.

[0117] When the entire second portion R3b is modified in step ST12, the second region R2 is selectively removed from the entire first region R1, the first portion R3a, and the second portion R3b in step ST14. Then, the entire modified second portion R3b is removed in step ST18. By selectively removing the second region R2 as described above without removing the entire third region R3 in step ST14, the exposure amount for obtaining the desired dimensions of the metal-containing layer ML can be further reduced in step ST18. That is, by modifying the entire second portion R3b in step ST12, the sensitivity can be further improved. Further, by modifying the entire second portion R3b in step ST12, the roughness of the developed metal-containing layer ML, for example, LWR (Line Width Roughness), can be reduced while further reducing the exposure amount as described above.

[0118] FIG. 11 is a flowchart of a development method according to one exemplary embodiment. The development method shown in FIG. 11 (hereinafter referred to as "method MT2") can be executed by the developing apparatus of the above embodiment. Method MT2 can be applied to the substrate W shown in FIG. 6. Method MT2 may include steps ST21 to ST29. Steps ST21 to ST29 can be executed in order. Method MT2 may not include at least one of steps ST23 and ST27 to ST29. Method MT2 may also be executed using the second processing station PS2 of the substrate processing system SS shown in FIG. 4. In method MT1, in the second processing station PS2, the dry development unit included in the development module PM6 is, for example, the heat treatment apparatus 100. In contrast, in method MT2, the dry development unit included in the development module PM6 is, for example, the plasma processing apparatus 1.

[0119] (Step ST21) In step ST21, the substrate W shown in FIG. 6 is provided. Step ST21 can be executed in the same manner as step ST11 of method MT1.

[0120] (Step ST22) As shown in FIG. 7, in step ST22, energy is supplied to the substrate W to modify a part R3b1 adjacent to the first part R3a in the second part R3b. Step ST22 can be executed in the same manner as step ST12 of method MT1. The process conditions in step ST22 may be the same as the process conditions in step ST12 of method MT1.

[0121] Step ST22 may include a step ST22a corresponding to step ST12a of method MT1 and a step ST22b corresponding to step ST12b of method MT1. Step ST22a can be executed in the same manner as step ST12a of method MT1. Step ST22b can be executed in the same manner as step ST12b of method MT1.

[0122] Also in method MT2, by heating the substrate W in step ST22, a part R3b1 adjacent to the first part R3a in the second part R3b is modified. That is, also in method MT2, at the end of step ST22, the third region R3 includes the modified part R3b1 and the unmodified remaining part R3b2.

[0123] (Step ST23) In step ST23, measurement on the substrate W is performed. Step ST23 can be executed in the same manner as step ST13 of method MT1.

[0124] (Step ST24) As shown in FIG. 8, in step ST24, a first processing gas is supplied into the chamber to selectively remove the second region R2 and the remaining portion R3b2 from the first region R1, the first partial region R3a, and a partial region R3b1. Step ST24 can be executed in the same manner as step ST14 of method MT1. Step ST24 may be performed in the development module PM6. That is, step ST24 may be performed in the plasma processing chamber 10 of the plasma processing apparatus 1. The process conditions in step ST24 may be the same as the process conditions in step ST14 of method MT1. In step ST24 as well, residues RD may occur in the same manner as in step ST14.

[0125] (Step ST25) As shown in FIG. 9, in step ST25, energy is supplied to the substrate W to modify the modified partial region R3b1 of the first region R1, the first partial region R3a, and the second partial region R3b. The process conditions in step ST25 may be the same as the process conditions in step ST17 of method MT1. Step ST25 may be performed in the development module PM6 in the same manner as step ST24. That is, step ST25 may be performed in the plasma processing chamber 10 of the plasma processing apparatus 1.

[0126] (Step ST26) As shown in FIG. 10, in step ST26, a second processing gas is supplied into the chamber to remove the modified partial region R3b1A of the second partial region R3b. Step ST26 can be executed in the same manner as step ST18 of method MT1. The process conditions in step ST26 may be the same as the process conditions in step ST18 of method MT1. Step ST26 may be performed in the development module PM6 in the same manner as steps ST24 and ST25. That is, step ST26 may also be performed in the plasma processing chamber 10 of the plasma processing apparatus 1.

[0127] (Step ST27) In step ST27, steps ST24 to ST26 are repeated.

[0128] (Step ST28) In step ST28, the substrate W is heated. Step ST28 can be executed in the same manner as step ST15 of method MT1. The process conditions in step ST28 may be the same as those in step ST15 of method MT1.

[0129] (Step ST29) Step ST29 performs measurements on the substrate W. In step ST29, similar to step ST23, the substrate W can be measured by the measurement module PM5. The measurement may be an optical measurement or other measurements. The control unit CT may determine the presence or absence of abnormalities such as defects, scratches, and foreign matter adhesion in the development pattern of the substrate W based on the appearance, dimensions, and / or pattern shape of the measured substrate W. If an abnormality is determined in the control unit CT, rework or discard of the substrate W may be performed.

[0130] Thus, in method MT2, a series of steps from step ST21 to step ST29 may be performed in the second processing station PS2. Steps ST24 to ST26 may be performed in the development module PM6 (the plasma processing chamber 10 of the plasma processing apparatus 1). That is, in method MT2, steps ST24 and ST26 may be performed in the same chamber.

[0131] Hereinafter, various experiments conducted for the evaluation of method MT1 and method MT2 will be described. The experiments described below do not limit the present disclosure.

[0132] (First Experiment) In the first experiment, a substrate was provided on the substrate support in the chamber. The substrate includes an underlayer film and a resist film on the underlayer film. The resist film contains tin oxide. The resist film has an exposed exposure region, a non-exposed non-exposure region, and an intermediate exposure region located between the exposure region and the non-exposure region. The intermediate exposure region includes a first intermediate exposure portion adjacent to the exposure region and a second intermediate exposure portion adjacent to the first intermediate exposure portion.

[0133] Subsequently, the substrate was heated at 180°C for 60 seconds in an atmospheric environment containing oxygen and water (PEB). Subsequently, the substrate was heated at 200°C for 90 seconds in an atmospheric environment containing oxygen and water (Add Bake). As a result, a part of the second intermediate exposure portion adjacent to the first intermediate exposure portion was modified.

[0134] Subsequently, boron trichloride gas was supplied into the chamber to develop the resist film. That is, the unmodified remainder of the non-exposed region and the second intermediate exposure region was selectively removed with respect to the exposed region, the first intermediate exposure portion, and the modified part of the second intermediate exposure portion. At this time, the pressure in the chamber was 500 mTorr, and the temperature of the substrate support portion supporting the substrate was 115°C.

[0135] Subsequently, O ２ The substrate was exposed to plasma generated from the gas to modify the exposed region, the first intermediate exposure portion, and the modified part of the second intermediate exposure portion. At this time, the pressure in the chamber was 100 mTorr, and the temperature of the substrate support portion supporting the substrate was 55°C.

[0136] Subsequently, the substrate was exposed to plasma generated from a processing gas containing hydrogen bromide gas, methane gas, and nitrogen gas in the chamber to remove the modified part of the second intermediate exposure portion. At this time, the pressure in the chamber was 10 mTorr, and the temperature of the substrate support portion supporting the substrate was 55°C. An electrical bias was applied to the substrate support portion.

[0137] (Second Experiment) In the second experiment, a substrate having the same structure as the substrate used in the first experiment was provided on the substrate support portion in the chamber. Subsequently, the resist film was developed by wet development in which the resist film was brought into contact with a developer.

[0138] (Third Experiment) In the third experiment, a substrate having the same structure as the substrate used in the first experiment was provided on the substrate support portion in the chamber. Subsequently, the substrate was heated. At this time, the pressure in the chamber was 7 Torr, and the temperature of the substrate support portion supporting the substrate was 200°C.

[0139] Thereafter, a mixed gas of hydrogen bromide gas and boron trichloride gas was supplied into the chamber to develop the resist film. At this time, the pressure in the chamber was 500 mTorr, and the temperature of the substrate support portion supporting the substrate was 60°C.

[0140] (First Experimental Result) In the first to third experiments, while changing the exposure amount, the dimensions (CD: Critical Dimension) of the resist pattern after development were measured. FIG. 12 is a graph showing an example of the relationship between the CD and the exposure amount in the first to third experiments. The horizontal axis of the graph indicates the exposure amount. The vertical axis of the graph indicates the CD. In FIG. 12, going in the positive direction of the horizontal axis indicates an increase in the exposure amount, and going in the positive direction of the vertical axis indicates an increase in the CD. In the graph, E1a, E2a, and E3a indicate the results of the first experiment, the second experiment, and the third experiment, respectively. As shown in FIG. 12, when trying to obtain the same CD, it can be seen that in the first experiment, the exposure amount is less compared to the second and third experiments. For example, in order to obtain x which is the desired CD, the exposure amount in the first experiment was 1.00, while the exposure amount in the second experiment was 1.06, and the exposure amount in the third experiment was 1.23. Here, each exposure amount for obtaining the above-mentioned desired CD in the first, second, and third experiments is the exposure amount normalized with the exposure amount in the first experiment being 1.00.

[0141] (Second Experimental Results) In the first to third experiments, while changing the exposure dose, the roughness (LWR) of the resist pattern after development was measured. FIG. 13 is a graph showing an example of the relationship between the LWR and the exposure dose in the first to third experiments. The horizontal axis of the graph indicates the exposure dose. The vertical axis of the graph indicates the LWR. In FIG. 13, moving in the positive direction of the horizontal axis indicates an increase in the exposure dose, and moving in the positive direction of the vertical axis indicates a large LWR. In the graph, E1b, E2b, and E3b indicate the results of the first experiment, the second experiment, and the third experiment, respectively. As shown in FIG. 13, it can be seen that even when the exposure dose is low, in the first experiment, the LWR does not deteriorate compared to the third experiment. Furthermore, when the exposure doses are the same at any exposure dose, it can be seen that in the first experiment, the LWR does not deteriorate compared to the third experiment.

[0142] (Fourth Experiment) In the fourth experiment, a substrate having the same structure as the substrate used in the first experiment was provided on the substrate support in the chamber. Then, in the same manner as in the first experiment, the substrate was heated in an air atmosphere. Then, the substrate was provided on another substrate support in another chamber.

[0143] Then, boron trichloride gas was supplied into the chamber to develop the resist film. At this time, the pressure in the chamber was 500 mTorr, and the temperature of the substrate support supporting the substrate was 115°C.

[0144] (Fifth Experiment) In the fifth experiment, the substrate obtained in the fourth experiment was taken out of the chamber and exposed in an air atmosphere. Then, the substrate was provided on another substrate support in another chamber.

[0145] Then, the substrate was exposed to plasma generated from a processing gas containing hydrogen bromide gas, methane gas, and nitrogen gas in the chamber. At this time, the pressure in the chamber was 10 mTorr, and the temperature of the substrate support supporting the substrate was 55°C. An electrical bias was applied to the substrate support.

[0146] (Experiment 6) In Experiment 6, a substrate having the same structure as the substrate used in Experiment 1 was provided on the substrate support in the chamber. Then, the substrate was heated. At this time, the pressure in the chamber was 7 Torr, and the temperature of the substrate support supporting the substrate was 200°C.

[0147] Then, a mixed gas of hydrogen bromide gas and boron trichloride gas was supplied into the chamber to develop the resist film. At this time, the pressure in the chamber was 500 mTorr, and the temperature of the substrate support supporting the substrate was 60°C.

[0148] (Results of Experiment 3) In Experiments 4 to 6, while changing the exposure amount, the dimensions (CD: Critical Dimension) of the resist pattern after development were measured. FIG. 14 is a graph showing an example of the relationship between the CD and the exposure amount in Experiments 4 to 6. The horizontal axis of the graph indicates the exposure amount. The vertical axis of the graph indicates the CD. In FIG. 14, moving in the positive direction of the horizontal axis indicates an increase in the exposure amount, and moving in the positive direction of the vertical axis indicates an increase in the CD. In the graph, E4, E5, and E6 indicate the results in Experiment 4, the results in Experiment 5, and the results in Experiment 6, respectively. As shown in FIG. 14, even when the above-mentioned partial modification of the second intermediate exposure portion and the above-mentioned partial removal of the second intermediate exposure portion are performed in different chambers, when trying to obtain the same CD, in Experiment 5, it can be seen that the exposure amount is less compared to Experiment 6. For example, in order to obtain a desired CD of y, the exposure amount was 1.00 in Experiment 5, whereas the exposure amount was 1.43 in Experiment 6. Here, each exposure amount for obtaining the above-mentioned desired CD in Experiments 5 and 6 is a value normalized with the exposure amount in Experiment 5 being 1.00. Therefore, it can be seen that even if the substrate is exposed to an air atmosphere, the exposure amount can be reduced.

[0149] (Fourth Experiment Results) In the fourth experiment, the LWR was 1.00, whereas in the fifth experiment, the LWR was 0.81. Here, each LWR in the fourth and fifth experiments is the LWR normalized with the LWR in the fourth experiment being 1.00. Also, residues were confirmed in the fourth experiment, but no residues were confirmed in the fifth experiment. Therefore, it can be seen that by exposing the substrate to the plasma generated from the processing gas containing hydrogen bromide gas, methane gas, and nitrogen gas, the LWR can be reduced and the residues can be removed.

[0150] As described above, various exemplary embodiments have been explained. However, without being limited to the above-described exemplary embodiments, various additions, omissions, substitutions, and changes may be made. Also, it is possible to form other embodiments by combining elements in different embodiments.

[0151] Here, various exemplary embodiments included in the present disclosure are described in [E1] to [E19] below.

[0152] [E1] (a) A step of providing a substrate on a substrate support portion in a chamber, wherein the substrate includes an underlying film and a metal-containing layer on the underlying film, and the metal-containing layer has an exposed first region, an unexposed second region, and a third region located between the first region and the second region, and the third region includes a first portion adjacent to the first region and a second portion adjacent to the first portion; (b) a step of supplying energy to the substrate to modify at least a part of the second portion adjacent to the first portion; (c) a step of supplying a first processing gas into the chamber to selectively remove the second region with respect to the modified at least a part of the first region, the first portion, and the second portion; (d) after (c), a step of supplying a second processing gas into the chamber to remove the modified at least a part of the second portion. The developing method includes these steps.

[0153] According to the developing method [E1], the exposure amount for obtaining a desired dimension can be reduced.

[0154] [E2] In the above (b), a part of the second part adjacent to the first part is modified; in the above (c), with respect to the first region, the first part, and the modified part of the second part, the unmodified remaining parts of the second region and the second part are removed; in the above (d), the modified part of the second part is removed. The developing method according to [E1].

[0155] [E3] The above (d) includes removing the residue generated in the above (c). The developing method according to [E1] or [E2].

[0156] [E4] Further includes the step of repeating the above (c) and the above (d). The developing method according to any one of [E1] to [E3].

[0157] [E5] Further includes the step of supplying energy to the substrate between the above (c) and the above (d) to modify at least a part of the modified parts of the first region, the first part, and the second part. The developing method according to [E1] or [E2].

[0158] [E6] In the above (f), the substrate is exposed to the plasma generated from the oxygen-containing gas. The developing method according to [E5].

[0159] [E7] Further includes the step of repeating the above (c), the above (f), and the above (d). The developing method according to [E4] or [E6].

[0160] [E8] The above (b) includes heating the substrate under two or more different conditions. The developing method according to any one of [E1] to [E7].

[0161] [E9] The (b) includes:(b1) a step of heating the substrate under a first condition, wherein the heating time under the first condition is a first heating time, and the heating temperature under the first condition is a first heating temperature;(b2) a step of heating the substrate under a second condition different from the first condition, wherein the heating time under the second condition is a second heating time longer than the first heating time, and the heating temperature under the second condition is a second heating temperature higher than the first heating temperature.The developing method according to [E8].

[0162] [E10] The (b) includes heating the substrate under a condition of 200 °C or higher and 60 seconds or longer. The developing method according to any one of [E1] to [E6].

[0163] [E11] The second processing gas includes at least one selected from the group consisting of hydrogen halide, carboxylic acid, and Lewis acid. The developing method according to any one of [E1] to [E10].

[0164] [E12] The second processing gas further includes a carbon-containing gas. The developing method according to [E11]. ​​​​​​​​​​​​​[E18] (a) providing a substrate on a substrate support in a chamber, the substrate comprising an undercoat film and a metal-containing layer on the undercoat film, the metal-containing layer having a first exposed region and a second unexposed region; (b) heating the substrate under first conditions; (c) after (b), heating the substrate under second conditions different from the first conditions, the heating time under the second conditions being longer than the heating time under the first conditions and the heating temperature under the second conditions being higher than the heating temperature under the first conditions; (d) after (c), exposing the substrate to a first process gas containing boron trichloride gas while heating the substrate at 60 to 200°C; (e) after (d), exposing the substrate to a first plasma generated from an oxygen-containing gas; (f) after (e), exposing the substrate to a second plasma generated from a second process gas containing hydrogen bromide gas, methane gas, and nitrogen gas while applying an electric bias to the substrate support.

[0171] [E19] A method for manufacturing a semiconductor device comprising: a chamber; and a substrate support for supporting a substrate in the chamber, the substrate comprising an undercoat film and a metal-containing layer on the undercoat film, the metal-containing layer having an exposed first region, an unexposed second region, and a third region located between the first region and the second region, the third region including a first portion adjacent to the first region and a second portion adjacent to the first portion; a gas supply unit configured to supply a first process gas and a second process gas into the chamber; an energy supply unit configured to supply energy to the substrate; and a control unit, wherein the control unit supplies the energy to the substrate to modify at least a portion of the second portion adjacent to the first portion, and supplies the first process gas into the chamber to selectively remove the second region with respect to the first region, the first portion, and the modified at least a portion of the second portion, a developing apparatus configured to control the gas supplier and the energy supplier to supply the second process gas into the chamber to remove the modified at least part of the second portion.

[0172] CT…control unit, 11, 121…substrate support unit, 170…gas supply unit, ML…metal containing layer, R1…first region, R2…second region, R3…third region, R3a…first portion, R3b…second portion, R3b1…a portion, R3b2…remaining portion, W…substrate.

Claims

1. A development method comprising: (a) providing a substrate on a substrate support in a chamber, the substrate comprising an underlayer and a metal-containing layer on the underlayer, the metal-containing layer having a first exposed region, a second unexposed region, and a third region located between the first and second regions, the third region including a first portion adjacent to the first region and a second portion adjacent to the first portion; (b) supplying energy to the substrate to modify at least a portion of the second portion adjacent to the first portion; (c) supplying a first process gas into the chamber to selectively remove the second region with respect to the first region, the first portion, and the modified at least portion of the second portion; and (d) after (c), supplying a second process gas into the chamber to remove the modified at least portion of the second portion.

2. The development method according to claim 1, wherein in (b), a portion of the second portion adjacent to the first portion is modified; in (c), unmodified remaining portions of the second region and the second portion are removed from the modified portions of the first region, the first portion, and the second portion; and in (d), the modified portion of the second portion is removed.

3. The developing method according to claim 1 or 2, wherein step (d) includes removing residues generated in step (c).

4. The development method according to claim 1 or 2, further comprising the step of: (e) repeating steps (c) and (d).

5. The development method according to claim 1 or 2, further comprising the step of: (f) supplying energy to the substrate between (c) and (d) to modify at least the modified portions of the first region, the first portion, and the second portion.

6. The developing method according to claim 5, wherein in step (f), the substrate is exposed to plasma generated from an oxygen-containing gas.

7. The development method of claim 5, further comprising the step of: (g) repeating steps (c), (f), and (d).

8. The developing method according to claim 1 or 2, wherein (b) includes heating the substrate under two or more conditions different from each other.

9. The development method according to claim 8, wherein (b) comprises: (b1) a step of heating the substrate under first conditions, wherein a heating time under the first conditions is a first heating time, and a heating temperature under the first conditions is a first heating temperature; and (b2) a step of heating the substrate under second conditions different from the first conditions, wherein a heating time under the second conditions is a second heating time that is longer than the first heating time, and a heating temperature under the second conditions is a second heating temperature that is higher than the first heating temperature.

10. The developing method according to claim 1 or 2, wherein step (b) includes heating the substrate at 200° C. or higher for 60 seconds or longer.

11. The developing method according to claim 1 or 2, wherein the second processing gas contains at least one selected from the group consisting of hydrogen halide, carboxylic acid, and Lewis acid.

12. The development method of claim 11, wherein the second process gas further comprises a carbon-containing gas.

13. The developing method according to claim 1 or 2, wherein in step (d), plasma is generated from the second processing gas.

14. The developing method according to claim 1 or 2, wherein in step (d), an electrical bias is applied to the substrate support.

15. The developing method according to claim 1 or 2, wherein in step (d), the substrate is irradiated with a gas cluster ion beam.

16. The developing method according to claim 1 or 2, wherein (c) and (d) are carried out in the same chamber.

17. The developing method according to claim 1 or 2, wherein steps (c) and (d) are carried out in different chambers.

18. (a) providing a substrate on a substrate support in a chamber, the substrate comprising an undercoat film and a metal-containing layer on the undercoat film, the metal-containing layer having a first exposed region and a second unexposed region; (b) heating the substrate under first conditions; (c) after (b), heating the substrate under second conditions different from the first conditions, the heating time under the second conditions being longer than the heating time under the first conditions and the heating temperature under the second conditions being higher than the heating temperature under the first conditions; (d) after (c), exposing the substrate to a first process gas containing boron trichloride gas while heating the substrate at 60-200°C; (e) after (d), exposing the substrate to a first plasma generated from an oxygen-containing gas; (f) after (e), exposing the substrate to a second plasma generated from a second process gas containing hydrogen bromide gas, methane gas, and nitrogen gas while applying an electric bias to the substrate support.

19. A method for manufacturing a semiconductor device, comprising: a chamber; and a substrate support for supporting a substrate in the chamber, the substrate comprising an undercoat film and a metal-containing layer on the undercoat film, the metal-containing layer having a first exposed region, a second unexposed region, and a third region located between the first region and the second region, the third region including a first portion adjacent to the first region and a second portion adjacent to the first portion; a gas supply configured to supply a first process gas and a second process gas into the chamber; an energy supply configured to supply energy to the substrate; and a control unit, wherein the control unit supplies the energy to the substrate to modify at least a portion of the second portion adjacent to the first portion, and supplies the first process gas into the chamber to selectively remove the second region relative to the first region, the first portion, and the modified at least a portion of the second portion. a developing apparatus configured to control the gas supplier and the energy supplier to supply the second process gas into the chamber to remove the modified at least part of the second portion.

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