Substrate processing method and substrate processing system

Abstract

Provided is a technique capable of improving the surface roughness of a metal-containing resist film formed on a substrate. The substrate processing method includes: a step (ST1) of providing a substrate including a base film and a metal-containing resist film forming a pattern on the base film; a step (ST2) for forming a metal-containing film on the surface of the metal-containing resist film; and a step (ST3) for removing at least a portion of the metal-containing film together with a residue of the metal-containing film.

Description

Technical Field

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

[0002] Patent Document 1 discloses a method of forming a patterned thin film on a semiconductor substrate using extreme ultraviolet light (EUV).

[0003] Prior art literature

[0004] Patent Literature

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

[0006] The present disclosure provides a technology capable of improving the surface roughness of a metal-containing resist film formed on a substrate.

[0007] A substrate processing method in an exemplary embodiment of the present disclosure includes: (a) providing a substrate including a base film and a metal-containing resist film having a pattern formed on the base film; (b) forming a metal-containing film on a surface of the metal-containing resist film; and (c) removing at least a portion of the metal-containing film together with residues of the metal-containing film.

[0008] Effects of the Invention

[0009] According to an exemplary embodiment of the present disclosure, it is possible to provide a technology capable of improving the surface roughness of a metal-containing resist film formed on a substrate. BRIEF DESCRIPTION OF THE DRAWINGS

[0010] Figure 1 It is a diagram for explaining a configuration example of a plasma processing system.

[0011] Figure 2 It is a diagram for explaining a configuration example of a capacitively coupled plasma processing apparatus.

[0012] Figure 3 1 is a flowchart showing an example of a substrate processing method according to an exemplary embodiment.

[0013] Figure 4 This is a diagram showing an example of the cross-sectional structure of the substrate provided in step ST1.

[0014] Figure 5 It is an explanatory diagram schematically showing an example of the XX cross section of the metal-containing resist film in each step ST1, ST2, and ST3.

[0015] Figure 61 is a diagram showing an example of a cross-sectional structure of a substrate on which a metal film is formed in step ST2 .

[0016] Figure 7 This is a flowchart showing an example of step ST2 using the ALD method.

[0017] Figure 8 It is an explanatory diagram schematically showing an example of a phenomenon occurring on the surface of the substrate in steps ST21 to ST24 .

[0018] Fig. 9 This is a diagram showing an example of a cross-sectional structure of a substrate including a metal film after etching in step ST3.

[0019] Fig.10 This is a flowchart showing an example of step ST3 using the ALE method.

[0020] Fig.11 It is an explanatory diagram schematically showing an example of a phenomenon occurring on the surface of the substrate in steps ST31 to ST34 .

[0021] Fig.12 This is a flowchart showing an example of a substrate processing method including step ST5.

[0022] Fig.13 1 is a diagram showing an example of a cross-sectional structure of a substrate after the base film is etched in step ST5 .

[0023] Fig.14 This is a side view for explaining a structural example of a semi-batch plasma processing apparatus.

[0024] Fig.15 This is a top view for explaining an example of the internal structure of a semi-batch plasma processing apparatus.

[0025] Description of Reference Numerals

[0026] 1…plasma processing device; 2…control unit; 10…plasma processing chamber; 10s…plasma processing space; 11…substrate support unit; 13…shower head; UF…base film; RF…metal-containing resist film; MF…metal-containing film; W…substrate. DETAILED DESCRIPTION

[0027] Hereinafter, each embodiment of the present disclosure will be described.

[0028] In an exemplary embodiment, a substrate processing method is provided, comprising: (a) providing a substrate comprising a base film and a metal-containing resist film having a pattern formed on the base film; (b) forming a metal-containing film on a surface of the metal-containing resist film; and (c) removing at least a portion of the metal-containing film together with residues of the metal-containing film.

[0029] In one exemplary embodiment, the metal-containing resist film includes at least one metal selected from the group consisting of Sn, Hf, and Ti.

[0030] In one exemplary embodiment, the metal-containing resist film includes Sn.

[0031] In one exemplary embodiment, the metal-containing resist film is formed using EUV photolithography.

[0032] In one exemplary embodiment, for the (b) process, the metal-containing film is formed by ALD.

[0033] In an exemplary embodiment, the process (b) includes: (b1) supplying a first gas containing a metal-containing precursor to the surface of the metal-containing resist film to form a metal-containing precursor film; and (b2) reacting a second gas containing an oxidizing gas with the metal-containing precursor film to form a metal-containing film from the metal-containing precursor film.

[0034] In one exemplary embodiment, for the step (b2), plasma is generated from the second gas.

[0035] In one exemplary embodiment, the steps (b1) and (b2) are repeated.

[0036] In one exemplary embodiment, in the (b) process, the (b1) process ends before the metal-containing precursor film is formed on the entire surface of the metal-containing resist film, and / or the (b2) process ends before the reaction of the second gas with the metal-containing precursor film is completed.

[0037] In one exemplary embodiment, the metal-containing precursor film comprises a metal complex.

[0038] In one exemplary embodiment, the metal-containing precursor film includes the same metal as the metal included in the metal-containing resist film.

[0039] In an exemplary embodiment, the oxidizing gas includes at least one selected from the group consisting of oxygen, ozone, water, hydrogen peroxide, and nitrogen tetroxide.

[0040] In one exemplary embodiment, for the (b) process, the metal-containing film is formed by CVD.

[0041] In one exemplary embodiment, in the step (b), the metal-containing film is formed by a mixed gas of a metal-containing gas and an oxidizing gas.

[0042] In one exemplary embodiment, in the step (b), plasma is generated from the mixed gas to form the metal-containing film.

[0043] In one exemplary embodiment, for the (c) step, the metal-containing film is removed by ALE.

[0044] In an exemplary embodiment, the (c) process includes: (c1) modifying the metal-containing film using a third gas including a halogen gas; and (c2) removing the modified metal-containing film using a fourth gas including a removal precursor.

[0045] In one exemplary embodiment, the steps (c1) and (c2) are repeated.

[0046] In an exemplary embodiment, the halogen gas includes a fluorine-containing gas or a chlorine-containing gas.

[0047] In an exemplary embodiment, the removal precursor includes at least one selected from the group consisting of β-diketone and a chlorine-containing compound.

[0048] In one exemplary embodiment, the steps (b) and (c) are repeated.

[0049] In one exemplary embodiment, the (b) step and the (c) step are performed in the same chamber.

[0050] In one exemplary embodiment, the substrate processing method further includes (d) etching the base film.

[0051] In one exemplary embodiment, the steps (b), (c), and (d) are performed in the same chamber.

[0052] In one exemplary embodiment, the base film includes at least one selected from the group consisting of a silicon-containing film, a carbon-containing film, and a metal-containing film.

[0053] In one exemplary embodiment, a substrate processing system is provided, including a substrate processing apparatus having a chamber and a control unit, wherein the control unit performs the following control:

[0054] (a) preparing a substrate including a base film and a metal resist film having a pattern formed on the base film;

[0055] (b) controlling the formation of a metal-containing film on the surface of the metal-containing resist film; and

[0056] (c) Control to remove at least a portion of the metal-containing film together with the residue of the metal-containing film.

[0057] Hereinafter, various embodiments of the present disclosure will be described in detail with reference to the accompanying drawings. In addition, the same reference numerals are used to mark the same or identical elements in the various drawings, and repeated descriptions are omitted. Unless otherwise specified, the positional relationships such as up, down, left, and right are described based on the positional relationships shown in the drawings. The dimensional ratios in the drawings do not represent the actual ratios, and the actual ratios are not limited to the illustrated ratios.

[0058] <Configuration Example of Plasma Processing System>

[0059] Hereinafter, a configuration example of a plasma processing system will be described. Figure 1 : is a diagram for illustrating a structural example of a plasma processing system. In one embodiment, the plasma processing system includes a plasma processing device 1 and a control unit 2. The plasma processing system is an example of a substrate processing system, and the plasma processing device 1 is an example of a substrate processing device. The plasma processing device 1 includes a plasma processing chamber (also simply referred to as a "chamber") 10, a substrate support portion 11, and a plasma generating portion 12. The plasma processing chamber 10 has a plasma processing space. In addition, the plasma processing chamber 10 has at least one gas supply port for supplying at least one processing gas to the plasma processing space and at least one gas exhaust port for exhausting gas from the plasma processing space. The gas supply port is connected to the gas supply portion 20 described later, and the gas exhaust port is connected to the exhaust system 40 described later. The substrate support portion 11 is arranged in the plasma processing space and has a substrate supporting surface for supporting a substrate.

[0060] The plasma generating section 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 also be a capacitively coupled plasma (CCP: Capacitively Coupled Plasma), an inductively coupled plasma (ICP: Inductively Coupled Plasma), an ECR plasma (Electron-Cyclotron-Resonance Plasma), a helicon wave excited plasma (HWP: Helicon Wave Plasma) or a surface wave plasma (SWP: Surface Wave Plasma), etc. In addition, various types of plasma generating sections including an alternating current plasma generating section and a direct current plasma generating section may also be used. In one embodiment, the alternating current signal (AC power) used in the alternating current plasma generating section has a frequency in the range of 100 kHz to 10 GHz. Therefore, the alternating current signal includes a radio frequency (RF) signal and a microwave signal. In one embodiment, the RF signal has a frequency in the range of 100 kHz to 150 MHz.

[0061] The control unit 2 processes computer executable instructions that cause the plasma processing device 1 to perform various processes described in the present disclosure. The control unit 2 can be configured to control the various elements of the plasma processing device 1 in a manner that performs the various processes described herein. In one embodiment, a part or all of the control unit 2 may be included in the plasma processing device 1. The control unit 2 may include, for example, a computer 2a. The computer 2a may include, for example, a processing unit (CPU: Central Processing Unit) 2a1, a storage unit 2a2, and a communication interface 2a3. The processing unit 2a1 can be configured to perform various control operations by reading a program from the storage unit 2a2 and executing the read program. The program can be stored in the storage unit 2a2 in advance, and can also be obtained via a medium when necessary. The obtained program is stored in the storage unit 2a2, and is read from the storage unit 2a2 by the processing unit 2a1 and executed. The medium can be various storage media that can be read in the computer 2a, or a communication line connected to the communication interface 2a3. The storage unit 2a2 may include RAM (Random Access Memory), ROM (Read Only Memory), HDD (Hard Disk Drive), SSD (Solid State Drive), or a combination thereof. The communication interface 2a3 may communicate with the plasma processing apparatus 1 via a communication line such as a LAN (Local Area Network).

[0062] Hereinafter, a configuration example of a capacitively coupled plasma processing apparatus will be described as an example of the plasma processing apparatus 1 . Figure 2 1 is a diagram for explaining a structural example of a capacitively coupled plasma processing apparatus. The capacitively coupled plasma processing apparatus 1 includes a plasma processing chamber 10, a gas supply unit 20, a power supply 30, and an exhaust system 40. In addition, the plasma processing apparatus 1 includes a substrate support unit 11 and a gas introduction unit. The gas introduction unit is configured to introduce at least one processing gas into the plasma processing chamber 10. The gas introduction unit includes a shower head 13. The substrate support unit 11 is disposed in the plasma processing chamber 10. The shower head 13 is disposed above the substrate support unit 11. In one embodiment, the shower head 13 constitutes at least a portion of the ceiling of the plasma processing chamber 10. The plasma processing chamber 10 has a plasma processing space 10s defined by the shower head 13, the side wall 10a of the plasma processing chamber 10, the bottom wall 10b, and the substrate support unit 11. The plasma processing chamber 10 is grounded. The shower head 13 and the substrate support unit 11 are electrically insulated from the frame of the plasma processing chamber 10.

[0063] The substrate support portion 11 includes a main body 111 and a ring assembly 112. The main body 111 has a central area 111a for supporting a substrate W and an annular area 111b for supporting the ring assembly 112. A wafer is an example of a substrate W. The annular area 111b of the main body 111 surrounds the central area 111a of the main body 111 in a plan view. The substrate W is arranged on the central area 111a of the main body 111, and the ring assembly 112 is arranged on the annular area 111b of the main body 111 in a manner of surrounding the substrate W on the central area 111a of the main body 111. Therefore, the central area 111a is also referred to as a substrate supporting surface for supporting the substrate W, and the annular area 111b is also referred to as a ring supporting surface for supporting the ring assembly 112.

[0064] In one embodiment, the main body 111 includes a base 1110 and an electrostatic chuck 1111. The base 1110 includes a conductive component. The conductive component of the base 1110 can function as a lower electrode. The electrostatic chuck 1111 is arranged on the base 1110. The electrostatic chuck 1111 includes a ceramic component 1111a and an electrostatic electrode 1111b arranged in the ceramic component 1111a. The ceramic component 1111a has a central area 111a. In one embodiment, the ceramic component 1111a also has an annular area 111b. In addition, the annular electrostatic chuck or other components surrounding the electrostatic chuck 1111 such as an annular insulating component may have an annular area 111b. In this case, the ring assembly 112 may be arranged on the annular electrostatic chuck or the annular insulating component, or on both the electrostatic chuck 1111 and the annular insulating component. In addition, a radio frequency or direct current electrode may also be arranged in the ceramic component 1111a. In this case, the RF or DC electrode functions as a lower electrode. When the bias RF signal or DC signal described later is connected to the RF or DC electrode, the RF or DC electrode is also referred to as a bias electrode. In addition, the conductive component of the base station 1110 and the RF or DC electrode can also function as two lower electrodes at the same time.

[0065] The ring assembly 112 includes one or more ring-shaped components. In one embodiment, the one or more ring-shaped components include one or more edge rings and at least one cover ring. The edge ring is formed of a conductive material or an insulating material, and the cover ring is formed of an insulating material.

[0066] In addition, the substrate support portion 11 may also include a temperature control module configured to adjust at least one of the electrostatic suction cup 1111, the ring assembly 112 and the substrate to a target temperature. The temperature control module may also include a heater, a heat transfer medium, a flow path 1110a or a combination thereof. In the flow path 1110a, a heat transfer fluid such as salt water or gas flows. In one embodiment, the flow path 1110a is formed in the base 1110, and one or more heaters are arranged in the ceramic part 1111a of the electrostatic suction cup 1111. In addition, the substrate support portion 11 may also include a heat transfer gas supply portion configured to supply a heat transfer gas between the back side of the substrate W and the central area 111a.

[0067] The showerhead 13 is configured to introduce at least one processing gas from the gas supply unit 20 into the plasma processing space 10s. The showerhead 13 has at least one gas supply port 13a, at least one gas diffusion chamber 13b, and a plurality of gas introduction ports 13c. The processing gas supplied to the gas supply port 13a is introduced into the plasma processing space 10s from the plurality of gas introduction ports 13c through the gas diffusion chamber 13b. In addition, the showerhead 13 includes an upper electrode. In addition, the gas introduction unit may also include one or more side gas injection units (SGI: Side Gas Injector) installed in one or more openings formed on the side wall 10a in addition to the showerhead 13.

[0068] The gas supply unit 20 may also include at least one gas source 21 and at least one flow controller 22. In one embodiment, the gas supply unit 20 is configured to supply at least one processing gas to the nozzle 13 via the corresponding gas sources 21 via the corresponding flow controllers 22. Each flow controller 22 may also include a mass flow controller or a pressure-controlled flow controller. In addition, the gas supply unit 20 may also include one or more flow modulation devices for modulating or pulsing the flow of at least one processing gas.

[0069] The power supply 30 includes a radio frequency power supply 31 coupled to the plasma processing chamber 10 via at least one impedance matching circuit. The radio frequency power supply 31 is configured to supply at least one radio frequency signal (radio frequency power) such as a source radio frequency signal and a bias radio frequency signal to at least one lower electrode and / or at least one upper electrode. Thus, plasma is formed by at least one processing gas supplied to the plasma processing space 10s. Thus, the radio frequency power supply 31 can function as at least a part of the plasma generating unit 12. In addition, by supplying a bias radio frequency signal to at least one lower electrode, a bias potential can be generated on the substrate W, and ion components in the formed plasma can be introduced into the substrate W.

[0070] In one embodiment, the RF power supply 31 includes a first RF generating unit 31a and a second RF generating unit 31b. The first RF generating unit 31a is configured to couple with at least one lower electrode and / or at least one upper electrode via at least one impedance matching circuit to generate a source RF signal (source RF power) for plasma generation. In one embodiment, the source RF signal has a frequency in the range of 10 MHz to 150 MHz. In one embodiment, the first RF generating unit 31a may also be configured to generate a plurality of source RF signals with different frequencies. The generated one or more source RF signals are supplied to at least one lower electrode and / or at least one upper electrode.

[0071] The second RF generating unit 31b is configured to couple with at least one lower electrode via at least one impedance matching circuit to generate a bias RF signal (bias RF power). The frequency of the bias RF signal may be the same as or different from the frequency of the source RF signal. In one embodiment, the bias RF signal has a frequency lower than the frequency of the source RF signal. In one embodiment, the bias RF signal has a frequency in the range of 100kHz to 60MHz. In one embodiment, the second RF generating unit 31b may also be configured to generate a plurality of bias RF signals with different frequencies. The generated one or more bias RF signals are supplied to at least one lower electrode. In addition, in various embodiments, at least one of the source RF signal and the bias RF signal may be pulsed.

[0072] In addition, the power supply 30 may also include a DC power supply 32 coupled to the plasma processing chamber 10. The DC power supply 32 includes a first DC generating unit 32a and a second DC generating unit 32b. In one embodiment, the first DC generating unit 32a is configured to be connected to at least one lower electrode to generate a first DC signal. The generated first DC signal is applied to at least one lower electrode. In one embodiment, the second DC generating unit 32b is configured to be connected to at least one upper electrode to generate a second DC signal. The generated second DC signal is applied to at least one upper electrode.

[0073] In various embodiments, the first and second DC signals may be pulsed. In this case, a sequence of DC-based voltage pulses is applied to at least one lower electrode and / or at least one upper electrode. The voltage pulse may also have a rectangular, trapezoidal, triangular or a combination thereof pulse waveform. In one embodiment, a waveform generator for generating a sequence of voltage pulses from a DC signal is connected between the first DC generator 32a and at least one lower electrode. Therefore, the first DC generator 32a and the waveform generator constitute a voltage pulse generator. In the case where the second DC generator 32b and the waveform generator constitute a voltage pulse generator, the voltage pulse generator is connected to at least one upper electrode. The voltage pulse may have either a positive polarity or a negative polarity. In addition, the sequence of voltage pulses may also include one or more positive polarity voltage pulses and one or more negative polarity voltage pulses in one cycle. In addition, the first and second DC generators 32a, 32b may be provided in addition to the RF power supply 31, or the first DC generator 32a may be provided instead of the second RF generator 31b.

[0074] The exhaust system 40 can be connected to a gas outlet 10e, for example, provided at the bottom of the plasma processing chamber 10. The exhaust system 40 can also include a pressure regulating valve and a vacuum pump. The pressure in the plasma processing space 10s is regulated by the pressure regulating valve. The vacuum pump can also include a turbomolecular pump, a dry pump, or a combination thereof.

[0075] <An Example of Substrate Processing Method>

[0076] Figure 3 1 is a flowchart showing an example of a substrate processing method (hereinafter also referred to as "the present processing method") according to an exemplary embodiment. Figure 3 As shown in FIG. 1 , the processing method includes a step ST1 of providing a substrate including a metal-containing resist film, a step ST2 of forming a metal-containing film on the surface of the metal-containing resist film, and a step ST3 of etching the metal-containing film. The processing method may also include a determination step ST4. The processing in each step may be performed at Figure 1 Hereinafter, the processing method will be described by taking the case where the control unit 2 controls each part of the plasma processing apparatus 1 to execute the processing method on the substrate W as an example.

[0077] (Step ST1: Providing a Substrate)

[0078] In one embodiment, in step ST1 , a substrate W is provided in the chamber 10 of the plasma processing apparatus 1 . The substrate W is provided on the central region 111 a of the substrate support 11 . The substrate W is held on the substrate support 11 by the electrostatic chuck 1111 .

[0079] After the substrate W is arranged in the central area 111a of the substrate support part 11, the temperature of the substrate support part 11 can be adjusted to a set temperature by a temperature control module. The set temperature can be, for example, a temperature below 300°C, or a temperature above 100°C and below 300°C (in one example, room temperature). In one example, adjusting or maintaining the temperature of the substrate support part 11 includes adjusting or maintaining the temperature of the heat transfer fluid flowing through the flow path 1110a at a set temperature or a temperature different from the set temperature. In one example, adjusting or maintaining the temperature of the substrate support part 11 includes controlling the pressure of the heat transfer gas (for example, He) between the electrostatic chuck 1111 and the back of the substrate W. In addition, the timing when the heat transfer fluid starts to flow to the flow path 1110a can be before or after the substrate W is placed on the substrate support part 11, or at the same time. In addition, in the present processing method, the temperature of the substrate support part 11 can be adjusted to the set temperature before step ST1. That is, the substrate W can be prepared in the substrate support part 11 after the temperature of the substrate support part 11 is adjusted to the set temperature. In one embodiment, in the subsequent steps of the present processing method, the temperature of the substrate supporting portion 11 is maintained at the set temperature adjusted in step ST1 .

[0080] Figure 4 1 is a diagram showing an example of a cross-sectional structure of a substrate W provided in step ST1. Figure 4 As shown, in one embodiment, the substrate W has a base film UF and a metal-containing resist film RF formed on the base film UF. The substrate W can be used to manufacture semiconductor devices. The semiconductor devices include storage devices and logic devices such as DRAM, 3D-NAND flash memory, etc.

[0081] The bottom film UF may include at least one selected from the group consisting of a silicon-containing film, a carbon-containing film, and a metal-containing film. The bottom film UF is not limited to one layer, but may also be multiple layers. The bottom film UF may be two or three layers. The bottom film UF may have a first layer, a second layer, and a third layer from top to bottom. The first layer of the bottom film UF may be a spin-on glass (SOG) film, a SiC film, a SiON film, a Si-containing anti-reflection film (SiARC), or an organic film. The second layer may be a spin-on carbon (SOC) film, an amorphous carbon film, or a silicon-containing film. The third layer may be a silicon-containing film. The silicon-containing film may be a silicon oxide film, a silicon nitride film, a silicon nitride film, a silicon carbonitride film, a polycrystalline silicon film, or a carbon-containing silicon film. The third layer may be formed by stacking a plurality of silicon-containing films. For example, the third layer may be formed by alternately stacking silicon oxide films and silicon nitride films. In addition, the third layer may also be formed by alternately stacking silicon oxide films and polycrystalline silicon films. In addition, the third layer may also be a stacked film comprising a silicon nitride film, a silicon oxide film, and a polycrystalline silicon film. Alternatively, the third layer may be a stacked film of a silicon oxide film and a silicon carbonitride film. Alternatively, the third layer may be a stacked film including a silicon oxide film, a silicon nitride film, and a silicon carbonitride film.

[0082] The metal-containing resist film RF is a film containing metal. The metal-containing resist film RF may include at least one metal selected from the group consisting of Sn, Hf and Ti. In one example, the metal-containing resist film RF contains Sn and may include tin oxide (SnO) and tin hydroxide (Sn-OH bond). The metal-containing resist film RF may include organic matter.

[0083] The metal-containing resist film RF is formed into a prescribed pattern having concave and convex (concave part, convex part). The metal-containing resist film RF can be formed by a photolithography process. The metal-containing resist film RF can be a film (metal-containing EUV resist film) formed using EUV photolithography. In one embodiment, a metal-containing photoresist film is first formed on the base film UF. Then, the photoresist film is selectively irradiated with light (such as EUV light, etc.) via an exposure mask. Thus, an exposed first area and an unexposed second area are formed on the photoresist film. Then, the photoresist film is developed to remove an area (such as the second area) of the photoresist film, and a metal-containing resist film RF having a concave and convex pattern is formed. Step ST1 may include at least a portion of the process (film formation process, exposure process, development process, etc.) of forming the metal-containing resist film RF. At least a portion of the process of forming the metal-containing resist film RF can be performed in the plasma processing device 1.

[0084] Figure 5 Schematically shows the XX cross section (in XX) of the metal-containing resist film RF in each step ST1, ST2, and ST3 of the present processing method. Figure 4 An explanatory diagram of an example of a cross section taken along line XX shown in FIG. Figure 5 (a) in the figure shows an example of a cross section of a metal-containing resist film RF formed in step ST1. This example shows that a recess H1 is formed on the side of the metal-containing resist film RF. That is, this example shows that there is roughness on the surface of the metal-containing resist film RF. In addition, the recess H1 is simplified and emphasized for the purpose of explanation, and the size and shape are not limited to this. One of the purposes of this processing method is to improve the surface roughness of the metal-containing resist film RF such as the recess H1.

[0085] (Step ST2: Forming a Metal-Containing Film)

[0086] In one embodiment, in step ST2 , the metal-containing film MF is formed on the surface of the metal-containing resist film RF. Figure 6 1 is a diagram showing an example of a cross-sectional structure of the substrate W on which the metal film MF is formed in step ST2 . Figure 5(b) in the figure shows an example of a cross section of the metal-containing film MF formed in the process ST2. In the process ST2, the metal-containing film MF is formed on the surface of the metal-containing resist film RF, and at the same time, the recess H1 located on the side of the metal-containing resist film RF is filled. As a result, the surface of the metal-containing resist film RF is flattened and the roughness is improved. The metal-containing film MF may contain the same metal as the metal contained in the metal-containing resist film RF. The metal-containing film MF may contain a metal different from the metal contained in the metal-containing resist film RF. The metal-containing film MF may contain at least one metal selected from the group consisting of Sn, Hf and Ti. In one example, the metal-containing film MF may contain Sn.

[0087] The formation of the metal-containing film MF in step ST2 can be performed using various methods such as atomic layer deposition (hereinafter referred to as ALD method) and CVD method. Various methods of forming the metal-containing film MF will be described below.

[0088] (ALD method)

[0089] In one embodiment, in the ALD method, the metal-containing resist film RF formed on the surface of the substrate W forms the metal-containing film MF by self-controlled adsorption and reaction of a predetermined material. Figure 7 As shown, in one embodiment, step ST2 using the ALD method includes: a step ST21 of forming a metal-containing precursor film, a first purge step ST22, a step ST23 of forming a metal-containing film MF from the metal-containing precursor film, a second purge step ST24 and a determination step ST25. Figure 8 1 and 2 are explanatory diagrams schematically showing an example of a phenomenon occurring on the surface of the substrate W in the steps ST21 to ST24. In addition, the first purge step ST22 and the second purge step ST24 may or may not be performed.

[0090] In step ST21, if Figure 8As shown, a first gas G1 containing a metal-containing precursor is supplied to the surface of the metal-containing resist film RF to form a metal-containing precursor film PF. The metal-containing precursor may contain the same metal as the metal contained in the metal-containing resist film RF. The metal-containing resist film RF may contain Sn, and the metal-containing precursor may contain Sn. Examples of Sn-containing substances may include tin alkane compounds, oxygen-containing tin compounds, nitrogen-containing tin compounds, tin halides, and the like. Examples of tin alkane compounds may include tin alkane, tetramethyltin alkane, tributyltin alkane, phenyltrimethyltin alkane, tetravinyltin alkane, dimethyl dichlorotin alkane, butyltrichlorotin alkane, trichlorophenyltin alkane, and the like. Examples of oxygen-containing tin compounds may include tributyltin methylolate, tin tert-butoxide, dibutyltin diacetate, triphenyltin acetate, tributyltin oxide, triphenyltin acetate, triphenyltin hydroxide, butyl chloride dihydroxide, tin acetylacetonate, and the like. Examples of nitrogen-containing tin compounds may include dimethylaminotrimethyltin, tri(dimethylamino)tert-butyltin, trimethyltin azide, tetra(dimethylamino)tin, N,N'-di-tert-butyl-2,3-diamidebutanetin (II), etc. Examples of tin halides may include tin chloride, tin bromide, tin iodide, dimethyltin dichloride, butyltin trichloride, phenyltin trichloride, etc. In addition, the metal-containing precursor may include Hf, Ti, etc. In step ST21 of one embodiment, in a plasma processing device 1, a first gas G1 is supplied from a showerhead 13 into a chamber 10. Then, in the chamber 10, the metal-containing precursor of the first gas G1 is adsorbed on the surface of the metal-containing resist film RF to form a metal-containing precursor film PF. The metal-containing precursor film PF may be a metal complex. Examples of the metal complex may include aminotin, etc. The metal-containing precursor film PF may include a metal of the same type as the metal contained in the metal-containing resist film RF. Examples of the metal contained in the metal-containing precursor film PF may include Hf, Ti, and the like in addition to Sn.

[0091] In step ST21, plasma may be generated from the first gas G1. In this case, in the plasma processing apparatus 1, one or more radio frequency signals are supplied from the radio frequency power supply 31 to the upper electrode and / or the lower electrode to generate plasma in the plasma processing space 10s.

[0092] In step ST22, the gas in the chamber 10 is exhausted by the exhaust system 40. At this time, an inert gas or the like may be supplied to the substrate W. Thereby, an excessive gas including the metal precursor or the like is purged.

[0093] In step ST23, if Figure 8As shown, a second gas G2 containing an oxidizing gas is supplied to the surface of the metal-containing resist film RF, and the second gas G2 reacts with the metal-containing precursor film PF to form a metal-containing film MF from the metal-containing precursor film PF. The second gas G2 is a gas that reacts with the metal-containing precursor adsorbed on the surface of the metal-containing resist film RF. The oxidizing gas of the second reaction gas G2 may include at least one selected from the group consisting of oxygen, ozone, water, hydrogen peroxide water and nitrogen tetroxide. In step ST23, in the plasma processing device 1, the second gas G2 is supplied from the nozzle 13 to the chamber 10. Then, in the chamber 10, the second gas G2 reacts with the metal-containing precursor film PF to form the metal-containing film MF. In step ST23, plasma can be generated by the second gas G2. In this case, in the plasma processing device 1, one or more radio frequency signals are supplied from the radio frequency power supply 31 to the upper electrode and / or the lower electrode, and plasma is generated in the plasma processing space 10s. In addition, the plasma (remote plasma) generated outside the chamber can also be introduced into the chamber. In steps ST21 and ST23 , plasma may not be generated.

[0094] In step ST24, the gas in the chamber 10 is exhausted by the exhaust system 40. At this time, an inert gas or the like may be supplied to the substrate W. Thus, an excessive gas such as the second gas G2 is purged.

[0095] In process ST25, it is determined whether the prescribed condition for ending process ST2 is satisfied. The prescribed condition may be a predetermined number of times that the process from process ST21 to process ST24 is set as a cycle. The prescribed number may be 1 time, less than 5 times, more than 5 times, or more than 10 times. In process ST25, if it is determined that the prescribed condition is not satisfied, the process returns to process ST21, and if it is determined that the prescribed condition is satisfied, the process ST2 is ended. For example, the prescribed condition may also be a condition related to the size of the metal-containing resist film RF containing the metal-containing film MF after process ST24. That is, after process ST24, it may be determined whether the size of the metal-containing resist film RF (the thickness of the metal-containing film MF) reaches a prescribed value or range, and the cycle from process ST21 to process ST24 is repeated until the prescribed value or range is reached. The size of the metal-containing resist film RF may be measured using an optical measuring device.

[0096] (Subconformal ALD method)

[0097] In one embodiment, in a subconformal ALD method, in the ALD method, the process conditions are set in such a way that self-controlled adsorption or reaction is not completed on the surface of the substrate W, thereby forming the metal-containing film MF. In one embodiment, in the subconformal ALD method, at least one of the following processes (i) and (ii) is performed in the ALD method:

[0098] (i) before the metal-containing precursor film PF is formed on the entire surface of the metal-containing resist film RF, the step ST21 is terminated;

[0099] (ii) The step ST24 is terminated before the reaction between the second gas G2 and the metal-containing precursor film PF is completed.

[0100] Other processes in the subconformal ALD method may be the same as those in the above-mentioned ALD method. In the subconformal ALD method, plasma may be used or not used, similarly to the above-mentioned ALD method.

[0101] (CVD method)

[0102] In one embodiment, the metal-containing film MF is formed by a mixed gas of a metal-containing gas and an oxidizing gas in a CVD method. As an example, plasma is generated from the mixed gas to form the metal-containing film MF.

[0103] In one embodiment, a mixed gas containing a metal-containing gas and an oxidizing gas is supplied from a showerhead 13 in a plasma processing device 1 to a chamber 10. The metal-containing gas may contain the same metal as the metal contained in the metal-containing resist film RF. The metal-containing resist film RF may contain Sn, and the metal-containing gas may contain Sn. Examples of Sn-containing substances may include tin alkane compounds, oxygen-containing tin compounds, nitrogen-containing tin compounds, tin halide compounds, and the like. Examples of tin alkane compounds may include tin alkane, tetramethyltin alkane, tributyltin alkane, phenyltrimethyltin alkane, tetravinyltin alkane, dimethyldichlorotin alkane, butyltrichlorotin alkane, trichlorophenyltin alkane, and the like. Examples of oxygen-containing tin compounds may include tributyltin methylolate, tin tert-butylate, dibutyltin diacetate, triphenyltin acetate, tributyltin oxide, triphenyltin acetate, triphenyltin hydroxide, butyl chlorotin dihydroxide, tin acetylacetonate, and the like. Examples of nitrogen-containing tin compounds may include dimethylaminotrimethyltin, tris(dimethylamino)tert-butyltin, trimethyltin azide, tetrakis(dimethylamino)tin, N,N'-di-tert-butyl-2,3-diamidebutanetin(II), etc. Examples of tin halide compounds may include tin chloride, tin bromide, tin iodide, dimethyltin dichloride, butyltin trichloride, phenyltin trichloride, etc. The oxidizing gas may include at least one gas selected from the group consisting of oxygen, ozone, water, hydrogen peroxide, and nitrogen tetroxide.

[0104] Next, one or more radio frequency signals are supplied to the upper electrode and / or the lower electrode from the radio frequency power supply 31. A high frequency electric field is generated between the shower head 13 and the substrate support 11, and plasma is generated from the mixed gas in the plasma processing space 10s. Then, the metal or active species containing the metal generated in the plasma is adsorbed on the surface of the substrate W, and a metal-containing film MF is formed on the surface of the substrate W.

[0105] In the CVD method, the metal-containing film MF can be formed using heat (thermal CVD method) instead of plasma.

[0106] (Step ST3: Etching Metal-Containing Film)

[0107] In one embodiment, in step ST3 , the residue of the metal-containing film MF is etched (removed) together with at least a portion of the metal-containing film MF formed on the surface of the metal-containing resist film RF. Fig. 9 1 is a diagram showing an example of a cross-sectional structure of the substrate W after the metal film MF is etched in step ST3 . Figure 5 (c) in FIG. 1 shows an example of a cross section of a metal-containing resist film RF in which the metal-containing film MF is etched in step ST3. In step ST3, the metal-containing film MF located on the surface of the metal-containing resist film RF is removed uniformly with a predetermined width. In addition, in step ST3, the metal-containing film MF may be removed to expose the metal-containing resist film RF, in which case the metal-containing resist film RF returns to its original size before the metal-containing film MF is formed. In addition, the metal-containing film MF may be removed without exposing the metal-containing resist film RF, in which case the metal-containing resist film RF is larger than its original size before the metal-containing film MF is formed.

[0108] The etching of the metal-containing film MF in step ST3 can be performed using various methods such as atomic layer etching (hereinafter referred to as ALE) method, conventional plasma etching method, etc. Hereinafter, the case of using the ALE method will be described.

[0109] (ALE method)

[0110] In one embodiment, in the ALE method, a predetermined material is adsorbed on the metal-containing film MF formed on the surface of the substrate W and a modification reaction is performed to remove the modified portion, thereby etching the metal-containing film MF. Fig.10 As shown, in one embodiment, the step ST3 using the ALE method includes: a step ST31 of modifying the metal containing film MF, a first purge step ST32, a step ST33 of removing the modified metal containing film MF, a second purge step ST34 and a determination step ST35. Fig.11 1 is an explanatory diagram schematically showing an example of a phenomenon occurring on the surface of the substrate W in the steps ST31 to ST34. In addition, the first purge step ST32 and the second purge step ST34 may or may not be performed.

[0111] In step ST31, Fig.11As shown, a third gas G3 containing a halogen gas is supplied to the surface of the metal-containing film MF to modify the metal-containing film MF. The halogen gas may be a fluorine-containing gas or a chlorine-containing gas. The fluorine-containing gas may be a gas containing at least one selected from the group consisting of HF, XeF2, CF4, NF3, and SF6. Plasma may be generated by HF and XeF2, or may not be generated. Plasma may be generated by CF4, NF3, and SF6.

[0112] In one embodiment, in step ST31, in the plasma processing apparatus 1, the third gas G3 is supplied from the showerhead 13 to the chamber 10. Through step ST31, the halogen gas of the third gas G3 reacts with the metal-containing film MF to modify the metal-containing film MF. In step ST31, plasma may be generated from the third gas G3. In this case, in the plasma processing apparatus 1, one or more radio frequency signals are supplied from the radio frequency power supply 31 to the upper electrode and / or the lower electrode, and plasma is generated in the plasma processing space 10s.

[0113] In step ST32, the gas in the chamber 10 is exhausted by the exhaust system 40. At this time, an inert gas or the like may be supplied to the substrate W. Thus, the excess gas such as the third gas G3 is purged.

[0114] In step ST33, if Fig.11As shown, a fourth gas G4 containing a removal precursor is supplied to the surface of the modified metal-containing film MF to remove the metal-containing film MF. The removal precursor may be a compound that forms a volatile compound by chemically reacting with molecules on the surface of the modified metal-containing film MF. The removal precursor of the fourth reaction gas G4 may include at least one selected from the group consisting of β-diketone (e.g., acetylacetone, etc.) and chlorine-containing compounds. The removal precursor of the fourth reaction gas G4 may be a chlorine-containing metal precursor. Examples of chlorine-containing metal precursors may include DMAC (dimethylaluminum chloride: Al(CH3)2Cl), SiCl4, TiCl4, aluminum chloride (AlCl3), boron trichloride (BCl3), dichlorosilane (SiH2Cl2), trichlorosilane (SiHCl3), monochlorodimethylsilane (SiHCl(CH3)2), monochlorotrimethylsilane (SiCl(CH3)3), dichlorodimethylsilane (SiCl2(CH3)2), trichloromethylsilane (SiCl3(CH3)). In step ST33, in the plasma processing apparatus 1, the fourth gas G4 is supplied from the showerhead 13 into the chamber 10. In step ST33, the fourth gas G4 reacts with the modified metal-containing film MF to remove the metal-containing film MF. In step ST33, plasma may be generated from the fourth gas G4. In this case, in the plasma processing apparatus 1, one or more radio frequency signals are supplied from the radio frequency power supply 31 to the upper electrode and / or the lower electrode, and plasma is generated in the plasma processing space 10s.

[0115] In step ST34, the gas in the chamber 10 is exhausted by the exhaust system 40. At this time, an inert gas or the like may be supplied to the substrate W. Thus, the excess gas such as the fourth gas G4 is purged.

[0116] In step ST35, it is determined whether the prescribed condition for ending step ST3 is satisfied. The prescribed condition may be a predetermined number of times that the process from step ST31 to step ST34 is set as a cycle. The prescribed number may be 1 time, less than 5 times, more than 5 times, or more than 10 times. In step ST35, if it is determined that the prescribed condition is not satisfied, the process returns to step ST31, and if it is determined that the prescribed condition is satisfied, the process ST3 is ended. For example, the prescribed condition may also be a condition related to the size of the metal-containing resist film RF containing the residual metal-containing film MF after step ST34. That is, after step ST34, it can be determined whether the size of the metal-containing resist film RF containing the residual metal-containing film MF reaches a prescribed value or range, and the cycle from step ST31 to step ST34 is repeated until the prescribed value or range is reached. The size of the metal-containing resist film RF can be measured with an optical measuring device.

[0117] The step ST3 may be performed in the same chamber 10 of the plasma processing apparatus 1 as the step ST2 , or may be performed in another chamber 10 of the plasma processing apparatus 1 .

[0118] In process ST4, it is determined whether the prescribed conditions for terminating the present treatment method are met. The prescribed conditions may be a predetermined number of times that the process ST2 and process ST3 are set as a cycle. The prescribed number of times may be 1 time, multiple times, 2 times, 3 times, less than 5 times, 5 times or more, or 10 times or more. In process ST4, if it is determined that the prescribed conditions are not met, the process returns to process ST2, and if it is determined that the prescribed conditions are met, the present treatment method is terminated. For example, the prescribed conditions may also be conditions related to the size or surface roughness of the metal-containing resist film RF after process ST3. That is, after process ST3, it may be determined whether the size or surface roughness of the metal-containing resist film RF containing the residual metal-containing film MF reaches a prescribed value or range, and the cycle of process ST2 and process ST3 is repeated until the prescribed value or range is reached. The size or surface roughness of the metal-containing resist film RF may be measured using an optical measuring device.

[0119] According to the present exemplary embodiment, the present processing method includes: (a) providing a substrate W including a base film UF and a metal-containing resist film RF having a pattern formed on the base film UF (ST1); (b) forming a metal-containing film MF on the surface of the metal-containing resist film RF (ST2); (c) etching at least a portion of the metal-containing film MF (ST3). In this case, the concave portion H1 on the surface of the metal-containing resist film RF is filled with the metal-containing film MF, and then the excess metal-containing film MF is etched. Thus, the surface of the metal-containing resist film RF formed on the substrate W can be flattened, and the surface roughness of the metal-containing resist film RF can be improved.

[0120] In one embodiment, if Fig.12 As shown, the processing method may further include a step ST5 of etching the base film UF. In one embodiment, the step ST5 is performed after the steps S2, S3 and ST4. Fig.13 1 is a diagram showing an example of a cross-sectional structure of the substrate W after the base film UF is etched in step ST5 .

[0121] In one embodiment, in step ST5, the base film UF is etched using the metal-containing resist film RF as a mask. In step ST5, the portion of the base film UF that is not covered by the metal-containing resist film RF (the portion exposed in the opening (recess) OP of the metal-containing resist film RF) is etched in the depth direction. Step ST5 can be performed in the chamber 10 of the plasma processing device 1 that is the same as steps ST2 and ST3. In addition, step ST5 can also be performed in the chamber 10 of the plasma processing device 1 that is different from steps ST2 and ST3.

[0122] In step ST5, first, a processing gas is supplied from the shower head 13 in the plasma processing apparatus 1 into the chamber 10. The processing gas includes a gas for generating active species required for etching the base film UF.

[0123] Then, one or more radio frequency signals are supplied from the radio frequency power supply 31 to the upper electrode and / or the lower electrode. Thus, plasma is generated in the plasma processing space 10s by the processing gas. In addition, a bias signal may also be supplied to the lower electrode of the substrate support 11. By supplying a bias radio frequency signal to the lower electrode, a bias potential is generated on the substrate W, and the ion components in the formed plasma can be introduced into the substrate W. Thus, the etching of the bottom film UF can be promoted. In addition, the method for etching the bottom film UF is not particularly limited.

[0124] In addition, this treatment method Figure 2 In addition to the single-wafer plasma processing apparatus shown in the figure, the processing may also be performed by a semi-batch plasma processing apparatus. The semi-batch plasma processing apparatus may be configured to include, for example, a chamber including a plurality of regions arranged circumferentially relative to a central axis, and a substrate support portion configured to support a plurality of substrates W, wherein the substrate W passes through the plurality of regions in sequence as the substrate support portion rotates.

[0125] Fig.14 It is a side view for explaining a structural example of a semi-batch type plasma processing apparatus 1 a. Fig.15 FIG. 1 is a top view for explaining an example of the internal structure of a semi-batch plasma processing apparatus 1a. Fig.14 and Fig.15 In the figure, a part of the structure such as the gas inlet is omitted. Fig.14 and Fig.15As shown, the semi-batch plasma processing apparatus 1a can be configured to include: a chamber 10a including four regions R1 to R4 and a substrate support portion 11a configured to support four substrates W1 to W4. The regions R1 to R4 can be configured so that the processing gas supplied to each region and the gas exhausted from each region are not mixed. In the plasma processing apparatus 1a, the substrate support portion 11a supports the four substrates W1 to W4, and can pass through the first region R1 to the fourth region R4 in sequence by rotating around the central axis X. In addition, the plasma processing apparatus 1a can be configured to perform steps ST21 and ST22 in the first region R1, perform steps ST23 and ST24 in the second region R2, perform steps ST31 and ST32 in the third region R3, and perform steps ST33 and ST34 in the fourth region R4. In the plasma processing apparatus 1a, if the second region R2 where the step ST23 is performed and the fourth region R4 where the step ST33 is performed are provided with a plasma generating unit, the first region R1 and the third region R3 do not necessarily need to be provided with a plasma generating unit. According to this semi-batch plasma processing apparatus 1a, the time between each process can be shortened, and the throughput of processing the substrate W can be greatly improved.

[0126] The embodiments of the present disclosure also include the following aspects.

[0127] (Note 1)

[0128] A substrate processing method, comprising:

[0129] (a) providing a substrate comprising a base film and a metal resist film having a pattern formed on the base film;

[0130] (b) forming a metal-containing film on the surface of the metal-containing resist film; and

[0131] (c) A step of removing at least a portion of the metal-containing film together with residues of the metal-containing film.

[0132] (Note 2)

[0133] The substrate processing method according to Supplementary Note 1, wherein the metal-containing resist film contains at least one metal selected from the group consisting of Sn, Hf, and Ti.

[0134] (Note 3)

[0135] The substrate processing method according to Supplementary Note 1, wherein the metal-containing resist film contains Sn.

[0136] (Note 4)

[0137] The substrate processing method according to any one of Supplementary Notes 1 to 3, wherein the metal-containing resist film is formed using EUV lithography.

[0138] (Note 5)

[0139] The substrate processing method according to any one of Supplementary Notes 1 to 4, wherein in the step (b), the metal-containing film is formed by ALD.

[0140] (Note 6)

[0141] The substrate processing method according to any one of Supplementary Notes 1 to 4, wherein the step (b) comprises:

[0142] (b1) supplying a first gas containing a metal-containing precursor to the surface of the metal-containing resist film to form a metal-containing precursor film; and

[0143] (b2) A step of causing a second gas including an oxidizing gas to react with the metal-containing precursor film to form the metal-containing film from the metal-containing precursor film.

[0144] (Note 7)

[0145] The substrate processing method according to Supplementary Note 6, wherein in the step (b2), plasma is generated from the second gas.

[0146] (Note 8)

[0147] The substrate processing method according to Supplementary Note 6 or 7, wherein the step (b1) and the step (b2) are repeated.

[0148] (Note 9)

[0149] The substrate processing method according to any one of Supplementary Notes 6 to 8, wherein in the step (b),

[0150] The step (b1) is completed before the metal-containing precursor film is formed on the entire surface of the metal-containing resist film; and / or

[0151] The step (b2) is ended before the reaction of the second gas with the metal-containing precursor film is completed.

[0152] (Note 10)

[0153] The substrate processing method according to any one of Supplementary Notes 6 to 9, wherein the metal-containing precursor film contains a metal complex.

[0154] (Note 11)

[0155] The substrate processing method according to any one of Supplementary Notes 6 to 10, wherein the metal-containing precursor contains the same metal as the metal contained in the metal-containing resist film.

[0156] (Note 12)

[0157] The substrate processing method according to any one of Supplementary Notes 6 to 11, wherein the oxidizing gas includes at least one selected from the group consisting of oxygen, ozone, water, hydrogen peroxide, and nitrogen tetroxide.

[0158] (Note 13)

[0159] The substrate processing method according to any one of Supplementary Notes 1 to 4, wherein in the step (b), the metal-containing film is formed by CVD.

[0160] (Note 14)

[0161] The substrate processing method according to any one of Supplementary Notes 1 to 4, wherein in the step (b), the metal-containing film is formed by a mixed gas of a metal-containing gas and an oxidizing gas.

[0162] (Note 15)

[0163] The substrate processing method according to Supplementary Note 14, wherein in the step (b), plasma is generated from the mixed gas to form the metal-containing film.

[0164] (Note 16)

[0165] The substrate processing method according to any one of Supplementary Notes 1 to 15, wherein in the step (c), the metal-containing film is removed by ALE.

[0166] (Note 17)

[0167] The substrate processing method according to any one of Supplementary Notes 1 to 15, wherein the step (c) comprises:

[0168] (c1) a step of modifying the metal-containing film using a third gas containing a halogen gas; and

[0169] (c2) A step of removing the modified metal-containing film using a fourth gas containing a removal precursor.

[0170] (Note 18)

[0171] The substrate processing method according to Supplementary Note 17, wherein the step (c1) and the step (c2) are repeated.

[0172] (Note 19)

[0173] The substrate processing method according to Appendix 17 or 18, wherein the halogen gas includes a fluorine-containing gas or a chlorine-containing gas.

[0174] (Note 20)

[0175] The substrate processing method according to any one of Supplementary Notes 17 to 19, wherein the removal precursor contains at least one selected from the group consisting of β-diketone and chlorine-containing compounds.

[0176] (Note 21)

[0177] The substrate processing method according to any one of Supplementary Notes 1 to 20, wherein the step (b) and the step (c) are repeated.

[0178] (Note 22)

[0179] The substrate processing method according to any one of Supplementary Notes 1 to 21, wherein the step (b) and the step (c) are performed in the same chamber.

[0180] (Note 23)

[0181] The substrate processing method according to any one of Notes 1 to 22, wherein the substrate processing method further comprises: (d) a step of etching the base film.

[0182] (Note 24)

[0183] The substrate processing method according to Supplementary Note 23, wherein the step (b), the step (c) and the step (d) are performed in the same chamber.

[0184] (Note 25)

[0185] The substrate processing method according to Supplementary Note 23 or 24, wherein the base film includes at least one selected from the group consisting of a silicon-containing film, a carbon-containing film, and a metal-containing film.

[0186] (Note 26)

[0187] A substrate processing system comprises: a substrate processing device having a chamber and a control unit,

[0188] The control unit performs the following control:

[0189] (a) preparing a substrate including a base film and a metal-containing resist film having a pattern formed on the base film;

[0190] (b) controlling the formation of a metal-containing film on the surface of the metal-containing resist film; and

[0191] (c) Control of removing at least a portion of the metal-containing film together with the residue of the metal-containing film.

[0192] The above embodiments are described for the purpose of explanation and are not intended to limit the scope of the present disclosure. Various modifications can be made to the embodiments without departing from the scope and purpose of the present disclosure. For example, a part of the constituent elements in a certain embodiment can be added to other embodiments. In addition, a part of the constituent elements in a certain embodiment can be replaced with corresponding constituent elements in other embodiments.

Claims

1. A substrate processing method, comprising: (a) providing a substrate comprising a base film and a metal resist film having a pattern formed on the base film; (b) forming a metal-containing film on the surface of the metal-containing resist film; and (c) A step of removing at least a portion of the metal-containing film together with residues of the metal-containing film.

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

3. The substrate processing method according to claim 1, wherein: The metal-containing resist film contains Sn.

4. The substrate processing method according to claim 1, wherein: The metal-containing resist film is formed using EUV lithography.

5. The substrate processing method according to claim 1, wherein: In the step (b), the metal-containing film is formed by ALD.

6. The substrate processing method according to claim 1, wherein: The step (b) comprises: (b1) supplying a first gas containing a metal-containing precursor to the surface of the metal-containing resist film to form a metal-containing precursor film; and (b2) A step of causing a second gas including an oxidizing gas to react with the metal-containing precursor film to form the metal-containing film from the metal-containing precursor film.

7. The substrate processing method according to claim 6, wherein: In the step (b2), plasma is generated from the second gas.

8. The substrate processing method according to claim 6, wherein: The steps (b1) and (b2) are repeated.

9. The substrate processing method according to claim 6, wherein: In the step (b), The step (b1) is completed before the metal-containing precursor film is formed on the entire surface of the metal-containing resist film; and / or The step (b2) is ended before the reaction of the second gas with the metal-containing precursor film is completed.

10. The substrate processing method according to claim 6, wherein: The metal-containing precursor film comprises a metal complex.

11. The substrate processing method according to claim 6, wherein: The metal-containing precursor includes the same metal as the metal included in the metal-containing resist film.

12. The substrate processing method according to claim 6, wherein: The oxidizing gas includes at least one selected from the group consisting of oxygen, ozone, water, hydrogen peroxide, and nitrogen tetroxide.

13. The substrate processing method according to claim 1, wherein: In the step (b), the metal-containing film is formed by CVD.

14. The substrate processing method according to claim 1, wherein: In the step (b), the metal-containing film is formed by a mixed gas of a metal-containing gas and an oxidizing gas.

15. The substrate processing method according to claim 14, wherein: In the step (b), plasma is generated from the mixed gas to form the metal-containing film.

16. The substrate processing method according to claim 1, wherein: In the step (c), the metal-containing film is removed by ALE.

17. The substrate processing method according to claim 1, wherein: The step (c) comprises: (c1) a step of modifying the metal-containing film using a third gas containing a halogen gas; and (c2) A step of removing the modified metal-containing film using a fourth gas containing a removal precursor.

18. The substrate processing method according to claim 17, wherein: The (c1) step and the (c2) step are repeated.

19. The substrate processing method according to claim 17, wherein: The halogen gas includes a fluorine-containing gas or a chlorine-containing gas.

20. The substrate processing method according to claim 17, wherein: The removal precursor comprises at least one selected from the group consisting of β-diketone and chlorine-containing compounds.

21. The substrate processing method according to claim 1, wherein: The steps (b) and (c) are repeated.

22. The substrate processing method according to claim 21, wherein: The step (b) and the step (c) are performed in the same chamber.

23. The substrate processing method according to claim 1, wherein: The substrate processing method further includes: (d) a step of etching the base film.

24. The substrate processing method according to claim 23, wherein: The step (b), the step (c), and the step (d) are performed in the same chamber.

25. The substrate processing method according to claim 23, wherein: The base film includes at least one selected from the group consisting of a silicon-containing film, a carbon-containing film, and a metal-containing film.

26. A substrate processing system comprising: a substrate processing device having a chamber and a control unit, The control unit performs the following control: (a) preparing a substrate including a base film and a metal-containing resist film having a pattern formed on the base film; (b) controlling the formation of a metal-containing film on the surface of the metal-containing resist film; and (c) Control of removing at least a portion of the metal-containing film together with the residue of the metal-containing film.

Images