Substrate processing method and substrate processing apparatus

Abstract

In one exemplary embodiment, this substrate processing method includes: (a) a step of providing a substrate on a substrate support in a chamber, the substrate including a film and a metal-containing mask on the film, the metal-containing mask including at least one opening, and the substrate including halogen; and (b) a step of exposing the substrate to a treatment gas or plasma generated from the treatment gas to remove the halogen. In (b), the temperature of the substrate support is lower than 160°C.

Description

Substrate processing method and substrate processing apparatus

[0001] Exemplary embodiments of this disclosure relate to a substrate processing method and a substrate processing apparatus.

[0002] Patent Document 1 discloses a method for processing a semiconductor substrate. In this method, a photopatterned metal-containing resist is placed on a substrate layer of a semiconductor substrate in a process chamber. Next, the photopatterned metal-containing resist is developed by selectively removing a portion of the resist by exposure to a developing chemical containing a halide, thereby forming a resist mask.

[0003] Japanese Patent Publication No. 2022-538040

[0004] This disclosure provides a technology for removing halogens contained in a substrate.

[0005] In one exemplary embodiment, a substrate processing method includes (a) providing a substrate on a substrate support in a chamber, wherein the substrate comprises a film and a metal-containing mask on the film, the metal-containing mask comprising at least one opening, and the substrate containing a halogen; and (b) exposing the substrate to a treatment gas or plasma generated from the treatment gas to remove the halogen, wherein in (b), the temperature of the substrate support is less than 160°C.

[0006] According to one exemplary embodiment, a technique for removing halogens contained in a substrate is provided.

[0007] Figure 1 is a diagram showing a substrate processing apparatus according to one exemplary embodiment. Figure 2 is a diagram illustrating an example configuration of a plasma processing system. Figure 3 is a diagram illustrating an example configuration of an inductively coupled plasma processing apparatus. Figure 4 is a diagram showing a substrate processing apparatus according to one exemplary embodiment. Figure 5 is a flowchart of a substrate processing method according to one exemplary embodiment. Figure 6 is a cross-sectional view of an example substrate to which the method of Figure 5 may be applied. Figure 7 is a cross-sectional view showing one step of the substrate processing method according to one exemplary embodiment. Figure 8 is a cross-sectional view showing one step of the substrate processing method according to one exemplary embodiment. Figure 9 is a cross-sectional view showing one step of the substrate processing method according to one exemplary embodiment. Figure 10 is a graph showing an example of bromine atom concentration after exposure of a substrate to a treatment gas. Figure 11 is a graph showing an example of bromine atom concentration after exposure of a substrate to a treatment gas. Figure 12 is a graph showing an example of the relationship between bromine atom concentration and time after exposure of a substrate to a treatment gas. Figure 13 is a graph showing an example of bromine atom concentration after exposure of a substrate to a treatment gas. Figure 14 is a graph showing an example of the relationship between bromine atom concentration and time after exposure of a substrate to a treatment gas. Figure 15 is a graph showing an example of the relationship between bromine atom concentration and time after exposure of a substrate to a treatment gas. Figure 16 is a graph showing an example of the relationship between bromine atom concentration and time after exposure of a substrate to a treatment gas. Figure 17 is a graph showing an example of bromine atom concentration after exposure of a substrate to a treatment gas. Figure 18 is a flowchart of a substrate treatment method according to another exemplary embodiment. Figure 19 is a cross-sectional view of an example substrate to which the method of Figure 18 may be applied. Figure 20 is a cross-sectional view showing one step of a substrate treatment method according to another exemplary embodiment. Figure 21 is a cross-sectional view showing one step of a substrate treatment method according to another exemplary embodiment. Figure 22 is a cross-sectional view showing one step of a substrate treatment method according to another exemplary embodiment.

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

[0009] Figure 1 shows a substrate processing apparatus according to one exemplary embodiment. The substrate processing apparatus SPA shown in Figure 1 comprises a loader module LM, a load lock module LL, a plurality of process modules P1 to P6, a transport module TM, and a control unit 2. The substrate processing apparatus SPA may also comprise a single process module.

[0010] The loader module LM has a chamber. The pressure inside the chamber of the loader module LM is set to atmospheric pressure. The loader module LM has a transport device. The transport device is, for example, a transport robot and is controlled by the control unit 2. The transport device is configured to transport substrates through the chamber of the loader module LM.

[0011] The load lock module LL is located between the loader module LM and the transport module TM. The load lock module LL provides a pre-pressure chamber. The load lock module LL may be equipped with a heater and a treatment gas introduction mechanism.

[0012] The transport module TM is connected to the load lock module LL via a gate valve. The transport module TM has a transport chamber whose internal space is configured to be depressurized. The transport module TM has a transport device. The transport device is, for example, a transport robot and is controlled by the control unit 2. The transport device is configured to transport substrates through the transport chamber. The transport device can transport substrates between the load lock module LL and each of the process modules P1 to P6, and between any two process modules among the process modules P1 to P6.

[0013] Each of the process modules P1 to P6 is a device configured to perform a dedicated substrate processing. Process modules P1, P2, P5, and P6 may be the plasma processing apparatus 1 shown in Figures 2 and 3. Process modules P3 and P4 may be the substrate processing apparatus 1a shown in Figure 4.

[0014] Figure 2 is a diagram illustrating an example configuration of a plasma 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 substrate processing system, and the plasma processing apparatus 1 is an example of a substrate processing apparatus. The plasma processing apparatus 1 includes a plasma processing chamber 10, a substrate support unit 11, and a plasma generation unit 12. The plasma processing chamber 10 has a plasma processing space. The plasma processing chamber 10 also has at least one gas supply port for supplying at least one processing gas to the plasma processing space, and at least one gas outlet for discharging gas from the plasma processing space. The gas supply port is connected to a gas supply unit 20, which will be described later, and the gas outlet is connected to an exhaust system 40, which will be described later. The substrate support unit 11 is located in the plasma processing space and has a substrate support surface for supporting a substrate.

[0015] 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 (Electron Cyclotron Resonance) plasma, helicon wave excited plasma (HWP), or surface wave plasma (SWP), etc. Various types of plasma generation units, including AC (Alternating Current) plasma generation units and DC (Direct Current) plasma generation units, may also be used. In one embodiment, the AC signal (AC power) used in the AC plasma generation unit has a frequency in the range of 100 kHz to 10 GHz. Therefore, the AC signal includes an RF (Radio Frequency) signal and a microwave signal. In one embodiment, the RF signal has a frequency in the range of 100 kHz to 150 MHz.

[0016] The control unit 2 processes computer-executable instructions that cause the plasma processing apparatus 1 to perform the various processes described herein. The control unit 2 may be configured to control the elements of the plasma processing apparatus 1 to perform the various processes described herein. In one embodiment, part or all of the control unit 2 may be included in the plasma processing apparatus 1. The control unit 2 is implemented, for example, by a computer 2a. The control unit 2 may include a processing unit 2a1, a storage unit 2a2, and a communication interface 2a3. The functions realized by the processing unit 2a1 described herein may be implemented in a circuit or processing circuit, including a general-purpose processor, an application-specific processor, integrated circuits, ASICs (Application Specific Integrated Circuits), a CPU (Central Processing Unit), a conventional circuit, and / or a combination thereof, programmed to realize the described functions. The processor is considered to be a circuit or processing circuit, including transistors and other circuits. The processor may be a programmed processor that executes a program stored in the storage unit 2a2. This program may be pre-stored in the storage unit 2a2 or retrieved via a medium when needed. The acquired program is stored in the storage unit 2a2 and read from the storage unit 2a2 and executed by the processing unit 2a1. The medium may be various storage media readable by the computer 2a, or it may be 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 device 1 via a communication line such as a LAN (Local Area Network).In this disclosure, circuits, units, and means are hardware programmed to perform or configured to perform the functions described. Such hardware may be any hardware described in this disclosure, or any hardware known to be programmed to perform or execute the functions described. If such hardware is a processor that is considered to be a type of circuit, such circuit, means, or unit is a combination of hardware and software used to constitute such hardware and / or processor.

[0017] The following describes an example configuration of an inductively coupled plasma processing apparatus as an example of a plasma processing apparatus 1. Figure 3 is a diagram illustrating an example configuration of an inductively coupled plasma processing apparatus.

[0018] The inductively coupled plasma processing apparatus 1 includes a plasma processing chamber 10, a gas supply unit 20, a power supply system 30, and an exhaust system 40. The plasma processing chamber 10 includes a dielectric window 101. The plasma processing apparatus 1 also includes a substrate support unit 11, a gas introduction unit, and an antenna 14. The substrate support unit 11 is located inside the plasma processing chamber 10. The antenna 14 is located on or above the plasma processing chamber 10 (i.e., on or above the dielectric window 101). The plasma processing chamber 10 has a plasma processing space 10s defined by the dielectric window 101, the side walls 102 of the plasma processing chamber 10, and the substrate support unit 11. The plasma processing chamber 10 is grounded.

[0019] 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. A wafer is an example of a substrate W. The annular region 111b of the main body portion 111 surrounds the central region 111a of the main body portion 111 in a plan view. The substrate W is placed on the central region 111a of the main body portion 111, and the ring assembly 112 is placed 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 called the substrate support surface for supporting the substrate W, and the annular region 111b is also called the ring support surface for supporting the ring assembly 112.

[0020] In one embodiment, the main body 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 bias electrode. The electrostatic chuck 1111 is placed on the base 1110. The electrostatic chuck 1111 includes a ceramic member 1111a and an electrostatic chuck electrode 1111b placed within the ceramic member 1111a. The electrostatic chuck electrode 1111b is also called a clamping electrode. In one embodiment, the electrostatic chuck electrode 1111b is electrically connected or coupled to a chuck power supply. The chuck power supply may be a DC power supply or an AC power supply. The ceramic member 1111a has a central region 111a. In one embodiment, the ceramic member 1111a also has an annular region 111b. Furthermore, other members surrounding the electrostatic chuck 1111, such as an annular electrostatic chuck or an annular insulating member, may have an annular region 111b. In this case, the ring assembly 112 may be placed on the annular electrostatic chuck or the annular insulating member, or on both the electrostatic chuck 1111 and the annular insulating member. Also, at least one bias electrode, electrically connected or coupled to the power supply 31 and / or power supply 32 described later, may be placed inside the ceramic member 1111a. Furthermore, the conductive member of the base 1110 and the bias electrode inside the ceramic member 1111a may function as multiple bias electrodes. Also, the electrostatic chuck electrode 1111b may function as a bias electrode. Therefore, the substrate support portion 11 includes at least one bias electrode.

[0021] 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 covering ring. The edge rings are formed of a conductive or insulating material, and the covering rings are formed of an insulating material.

[0022] The substrate support section 11 may also include a temperature control module configured to adjust at least one of the electrostatic chuck 1111, the ring assembly 112, and the substrate to a target temperature. The temperature control module may include a heater, a heat transfer medium, a flow path 1110a, or a combination thereof. A heat transfer fluid such as brine or gas flows through the flow path 1110a. In one embodiment, the flow path 1110a is formed within the base 1110, and one or more heaters are arranged within the ceramic member 1111a of the electrostatic chuck 1111. The substrate support section 11 may also include a heat transfer gas supply section configured to supply heat transfer gas to the gap between the back surface of the substrate W and the central region 111a.

[0023] The gas introduction section is configured to introduce at least one processing gas from the gas supply section 20 into the plasma processing space 10s. In one embodiment, the gas introduction section includes a central gas injector (CGI) 13. The central gas injector 13 is located above the substrate support section 11 and is attached to a central opening formed in the dielectric window 101. The central gas injector 13 has at least one gas supply port 13a, at least one gas flow path 13b, and at least one gas inlet 13c. The processing gas supplied to the gas supply port 13a passes through the gas flow path 13b and is introduced into the plasma processing space 10s from the gas inlet 13c. In addition to or instead of the central gas injector 13, the gas introduction section may also include one or more side gas injectors (SGIs) attached to one or more openings formed in the side wall 102.

[0024] The gas supply unit 20 may include at least one gas source 21 and at least one flow controller 22. In one embodiment, the gas supply unit 20 is configured to supply at least one processing gas to the gas inlet from a corresponding gas source 21 via a corresponding flow controller 22. Each flow controller 22 may include, for example, a mass flow controller or a pressure-controlled flow controller. Furthermore, the gas supply unit 20 may include at least one flow modulation device that modulates or pulses the flow rate of at least one processing gas.

[0025] The power supply system 30 includes a power supply 31 that is electrically connected to or coupled to the plasma processing chamber 10. In one embodiment, the power supply 31 is electrically connected to or coupled to the plasma processing chamber 10 via at least one impedance matcher. The impedance matcher may be a mechanically controlled matcher or an electronically controlled matcher. The power supply 31 is configured to supply at least one RF signal (RF power) to at least one bias electrode and antenna 14. This generates plasma from at least one processing gas supplied to the plasma processing space 10s. Therefore, the power supply 31 can function as at least part of the plasma generation unit 12. Furthermore, by supplying a bias RF signal to at least one bias electrode, a bias potential is generated on the substrate W, and ions in the formed plasma can be drawn into the substrate W.

[0026] The power supply 31 includes a first RF generation unit 31a and a second RF generation unit 31b. The first RF generation unit 31a is electrically connected to or coupled to the antenna 14 and is configured to generate a source RF signal (source RF power) to generate plasma in the plasma processing space 10s. In one embodiment, the first RF generation unit 31a is electrically connected to or coupled to the antenna 14 via at least one impedance matcher. In one embodiment, the source RF signal has a frequency in the range of 10 MHz to 150 MHz. In one embodiment, the first RF generation unit 31a may be configured to generate a plurality of source RF signals having different frequencies. One or more generated source RF signals are supplied to the antenna 14.

[0027] The second RF generation unit 31b is electrically connected to or coupled to at least one bias electrode and is configured to generate a bias RF signal (bias RF power). In one embodiment, the second RF generation unit 31b is electrically connected to or coupled to at least one bias electrode via at least one impedance matcher. The frequency of the bias RF signal may be the same as or different from the frequency of the source RF signal. In one embodiment, the bias RF signal has a frequency lower than the frequency of the source RF signal. In one embodiment, the bias RF signal has a frequency in the range of 100 kHz to 60 MHz. In one embodiment, the second RF generation unit 31b may 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 bias electrode. In various embodiments, at least one of the source RF signal and the bias RF signal may be pulsed.

[0028] The power supply system 30 may also include a power supply 32 that is electrically connected to or coupled to the plasma processing chamber 10. The power supply 32 includes a voltage generation unit 32a. In one embodiment, the voltage generation unit 32a is electrically connected to or coupled to at least one bias electrode and is configured to generate a voltage signal. The generated voltage signal is applied to at least one bias electrode.

[0029] In various embodiments, the voltage signal may be pulsed. In this case, the voltage generation unit 32a functions as a voltage pulse generation unit configured to generate a sequence of voltage pulses. Thus, the sequence of voltage pulses is applied to at least one bias electrode. In one embodiment, the sequence of voltage pulses has multiple cycles, each cycle including a burst of voltage pulses in a first period and a constant reference voltage in a second period. That is, the burst of voltage pulses is repeated in the sequence of voltage pulses. The absolute value of the voltage level of the voltage pulse is greater than the absolute value of the voltage level of the reference voltage. The voltage pulse may have an arbitrary waveform having a rectangular, trapezoidal, triangular, or a combination thereof, and the arbitrary waveform may change over time. The voltage pulse may have positive or negative polarity. Furthermore, the sequence of voltage pulses may include one or more positive voltage pulses and one or more negative voltage pulses within one cycle. Note that the voltage generation unit 32a may be provided in addition to the power supply 31, or it may be provided in place of the second RF generation unit 31b.

[0030] The antenna 14 includes one or more coils. In one embodiment, the antenna 14 may include an outer coil and an inner coil arranged coaxially. In this case, the power supply 31 may be connected to both the outer coil and the inner coil, or to either the outer coil or the inner coil. In the former case, the same RF generation unit may be connected to both the outer coil and the inner coil, or separate RF generation units may be connected to the outer coil and the inner coil separately.

[0031] The exhaust system 40 may be connected to, for example, a gas outlet 10e located 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 regulating valve regulates the pressure in the plasma processing space 10s. The vacuum pump may include a turbomolecular pump, a dry pump, or a combination thereof.

[0032] Figure 4 shows a substrate processing apparatus according to one exemplary embodiment. The substrate processing apparatus 1a shown in Figure 4 may include a sealed chamber 10a for housing a substrate W. The chamber 10a is formed from, for example, aluminum or an aluminum alloy. The upper end of the chamber 10a is open. The upper end of the chamber 10a is closed by a lid 29 which forms the ceiling. An inlet / outlet 130 for the substrate W is provided in the side wall 28a of the chamber 10a, and the inlet / outlet 130 can be opened and closed by a gate valve 131.

[0033] The substrate processing apparatus 1a comprises a mounting table 132 on which a substrate W is placed horizontally, and a lifting mechanism 33 for raising and lowering the mounting table 132. The mounting table 132 is substantially cylindrical and has a mounting plate 34 on which the substrate W is placed directly, and a base block 35 that supports the mounting plate 34. A temperature control mechanism 36 for controlling the temperature of the substrate W is provided inside the mounting plate 34. The temperature control mechanism 36 may be configured to adjust the temperature of the mounting table 132, which is the substrate support part. The temperature control mechanism 36 has, for example, a pipeline (not shown) through which a temperature control medium (for example, water) circulates, and adjusts the temperature of the substrate W by performing heat exchange between the temperature control medium flowing in the pipeline and the substrate W. The lifting mechanism 33 is located outside the chamber 10a and has an actuator or the like for raising and lowering the mounting table 132. The mounting base 132 is provided with multiple lifting pins (not shown) that are movable up and down relative to the upper surface of the mounting plate 34, which are used when loading and unloading the substrate W into and out of the chamber 10a.

[0034] The interior of the chamber 10a is divided by a partition plate 37 into an upper plasma generation space P and a lower substrate processing space S. The plasma generation space P is the space where plasma is generated, and the substrate processing space S is the space where the substrate W is exposed to gas. The partition plate 37 functions as a so-called ion trap, suppressing the permeation of ions in the plasma from the plasma generation space P to the substrate processing space S when inductively coupled plasma is generated in the plasma generation space P. Outside the chamber 10a, a gas supply unit 38 is provided to supply processing gas into the chamber 10a. The gas supply unit 38 may include a liquid source and a vaporizer that vaporizes the liquid supplied from the liquid source. The liquid supplied from the liquid source to the vaporizer vaporizes in the vaporizer. The vaporized gas is supplied into the chamber 10a as processing gas. The substrate processing apparatus 1a also includes an exhaust mechanism 39, which has a vacuum pump and discharges the gas inside the substrate processing space S to the outside of the chamber 10a.

[0035] The substrate processing apparatus 1a is configured as an inductively coupled plasma etching apparatus using an RF antenna. The lid 29, which forms the ceiling of the chamber 10a, is formed from, for example, a circular quartz plate and is configured as a dielectric window. An annular RF antenna 140 is formed on the lid 29 for generating inductively coupled plasma in the plasma generation space P of the chamber 10a, and the RF antenna 140 is connected to a high-frequency power supply 42 via a matching unit 41. The high-frequency power supply 42 outputs high-frequency power at an arbitrary output value at a constant frequency (usually 13.56 MHz or higher) suitable for generating plasma by inductively coupled high-frequency discharge. The matching unit 41 has a reactance-variable matching circuit (not shown) for matching the impedance of the high-frequency power supply 42 side with the impedance of the load (RF antenna 140 and plasma).

[0036] Figure 5 is a flowchart of a substrate processing method according to one exemplary embodiment. The substrate processing method MT1 shown in Figure 5 (hereinafter referred to as "method MT1") can be performed by the substrate processing apparatus SPA of Figure 1. Method MT1 can be applied to a substrate W. Method MT1 may be performed by the plasma processing apparatus 1 of Figures 2 and 3, or by the substrate processing apparatus 1a of Figure 4.

[0037] Figure 6 is a cross-sectional view of an example substrate to which the method of Figure 5 may be applied. As shown in Figure 6, in one embodiment, the substrate W comprises an etching target film EL and a metal-containing resist ML on the etching target film EL. The metal-containing resist ML includes a non-exposure region R1 and an exposure region R2. The metal-containing resist ML may be a photoresist or an EUV exposure resist. The substrate W may further comprise a base region UR. The etching target film EL is positioned between the metal-containing resist ML and the base region UR.

[0038] The metal-containing resist ML may contain at least one metal selected from the group consisting of tungsten (W), molybdenum (Mo), titanium (Ti), tin (Sn), aluminum (Al), zirconium (Zr), hafnium (Hf), indium (In), ruthenium (Ru), gallium (Ga), and zinc (Zn). The metal-containing resist ML may further contain carbon and oxygen. The metal-containing resist ML may also contain oxides of the above metals.

[0039] The etchable film EL may include a carbon-containing film. The etchable film EL may include a single layer of carbon-containing film or a multilayer carbon-containing film. The carbon-containing film may include at least one selected from the group consisting of spin-on carbon (SOC), amorphous carbon, SiOC, polymer (e.g., BARC), and SiC. The carbon-containing film may be formed by CVD or by spin coating.

[0040] The base region UR may, in one example, be a silicon wafer or a film formed on a silicon wafer. Examples of films include organic films, dielectric films, metal films, semiconductor films, etc. The base region UR may be composed of multiple films stacked on top of each other.

[0041] Hereinafter, Method MT1 will be described with reference to Figures 1 to 9, taking as an example the case in which Method MT1 is applied to a substrate W using the substrate processing apparatus SPA of the above embodiment. Figures 7 to 9 are cross-sectional views showing one step of a substrate processing method according to one exemplary embodiment. When the substrate processing apparatus SPA is used, Method MT1 can be executed in the substrate processing apparatus SPA by the control unit 2 controlling each part of the substrate processing apparatus SPA. In Method MT1, as shown in Figures 3 and 4, the substrate W on the substrate support unit 11 or mounting table 132 located in the plasma processing chamber 10 or chamber 10a may be processed.

[0042] As shown in Figure 5, Method MT1 may include steps ST1 to ST4. Steps ST1 to ST4 may be performed in order. Step ST1 may include steps ST11 to ST14. Steps ST11 to ST14 may be performed in order. Method MT1 does not have to include at least one of steps ST3 or ST4. Step ST1 does not have to include at least one of steps ST12 to ST14, and does not have to include step ST14. Step ST14 may be performed simultaneously with step ST2. Method MT1 may include a bake step. The bake step may be performed between steps ST13 and ST2, after step ST2, between steps ST13 and ST2, and after step ST2. If method MT1 includes step ST14, the baking step may be performed before step ST14, after step ST14, or both before and after step ST14. Steps ST1 to ST4 may be performed in-situ (in the same chamber) or in-system (a system capable of transporting substrates under reduced pressure between different chambers). If steps ST1 to ST4 are performed in-system, step ST2 may be performed in a first chamber (e.g., chamber 10a in Figure 4), and steps ST1 and ST4 may be performed in a second chamber (e.g., plasma processing chamber 10 in Figure 3). The second chamber is different from the first chamber. Step ST12 may be performed in a third chamber (e.g., a heat treatment apparatus under reduced pressure or in air). Step ST14 may be performed in a fourth chamber (e.g., plasma processing chamber 10 in Figure 3). Step ST3 may be performed in an ADI (After Development Inspection) apparatus. If method MT1 includes a baking step, steps ST1 to ST4 and the baking step may be performed in-situ (in the same chamber) or in-system (a system capable of transporting substrates under reduced pressure between different chambers). The baking step may be performed in a standalone chamber.When the baking process is performed in-system, the baking process may be carried out in any of the first, second, third, and fourth chambers, or in a fifth chamber different from these chambers (for example, a heat treatment apparatus under reduced pressure or in air).

[0043] (Step ST11) In step ST11, for example, the substrate W shown in Figure 6 is provided on the substrate support portion 11 in the plasma processing chamber 10 shown in Figure 3. The metal-containing resist ML may be formed by exposing an unexposed metal-containing resist in an exposure apparatus. The exposure apparatus may be an EUV exposure apparatus.

[0044] (Step ST12) In step ST12, the substrate W may be removed from the exposure apparatus into the atmosphere and then baked in a heat treatment apparatus in the atmosphere. After baking, the substrate W may be transported to the substrate treatment apparatus SPA and placed on the substrate support part 11 in the plasma treatment chamber 10 in Figure 3. Alternatively, the substrate W may be transported from the exposure apparatus to the substrate treatment apparatus SPA under reduced pressure without being removed from the exposure apparatus into the atmosphere. In this case, the baking process is performed, for example, in a heat treatment apparatus under reduced pressure.

[0045] (Step ST13) In step ST13, the substrate W is exposed to a developer gas containing halogen to develop the metal-containing resist ML. Alternatively, the substrate W may be exposed to a plasma generated from the developer gas containing halogen to develop the metal-containing resist ML. Dry development forms a metal-containing mask MK including at least one aperture OP, as shown in Figure 7. The surface OPa defining the aperture OP is the side wall of the metal-containing resist ML. The aperture OP may be formed by removing the unexposed region R1 or by removing the exposed region R2. The aperture OP may have a line pattern, a hole pattern, or a pillar pattern. The dimensions of the aperture OP (CD: Critical Dimension) may be 100 nm or less, or 30 nm or less.

[0046] The developing gas may contain at least one selected from the group consisting of hydrogen bromide (HBr), hydrogen fluoride (HF), hydrogen chloride (HCl), hydrogen iodide (HI), boron trichloride (BCl ３ ), boron tribromide (BBr ３ ), boron trifluoride (BF ３ ), chlorine (Cl ２ ), bromine (Br ２ ), halomethane, halogen-containing carboxylic acid, and halogen-containing organic acid. The halomethane may contain at least one selected from the group consisting of CH ｘ F ｙ , CH ｘ Cl ｙ , CH ｘ Br ｙ and CH ｘ I ｙ . Each of x and y is a natural number. The halogen-containing carboxylic acid may contain at least one selected from the group consisting of trichloroacetic acid (CCl ３ COOH), monofluoroacetic acid (CFH ２ COOH), difluoroacetic acid (CF ２ HCOOH), trifluoroacetic acid (CF ３ COOH), and chloro-difluoroacetic acid (CClF ２ COOH). The halogen-containing organic acid other than the halogen-containing carboxylic acid may contain β-dicarbonyl compounds such as trichloroacetylacetone (CCl ３ C(O)CH ２ C(O)CH ３ ), hexachloroacetylacetone (CCl ３ C(O)CH ２ C(O)CCl ３ ), trifluoroacetylacetone (CF ３ C(O)CH ２ C(O)CH ３ ), hexafluoroacetylacetone (HFAc, CF ３ C(O)CH ２ C(O)CF ３ ), etc.

[0047] After the completion of step ST12, halogen HR may remain on the substrate W. Halogen HR may also remain on the metal-containing mask MK. Halogen HR may also remain inside the metal-containing mask MK. Halogen HR may be a compound containing a metal contained in the metal-containing resist ML and a halogen contained in the developing gas.

[0048] (Step ST14) In step ST14, the substrate W is descammed. In step ST14, the scum may be removed from the surface of the metal-containing mask MK and the surface of the film EL to be etched by plasma generated from the processing gas. In step ST14, the surface of the metal-containing mask MK and the surface of the film EL to be etched may be smoothed. The processing gas in step ST14 may contain halogen-containing gases, such as hydrogen bromide (HBr), hydrogen chloride (HCl), and chlorine (Cl). ２ The process gas may include at least one selected from the group consisting of ). ４ ), nitrogen (N ２ ) and argon may further include at least one selected from the group. Examples of process gases are HBr and N ２ A mixed gas of HBr and CH ４ and N ２ A mixed gas with Cl ２ and CH ４ and N ２ It contains a mixed gas.

[0049] (Step ST2) In step ST2, the substrate W is exposed to a treatment gas to remove halogen HR (see Figure 8). The reaction between the treatment gas and halogen HR generates volatile halogen-containing substances. As a result, halogen HR is removed. For example, halogen HR bonded to metal in the substrate W may be replaced by oxygen atoms or hydroxyl groups with an oxygen-containing gas, and the halogen HR-containing substance may volatilize. For example, bromine bonded to tin in the substrate W may be replaced by hydrogen peroxide gas or H ２ It reacts with O gas, SnO ｘ Alternatively, SnOH and volatile bromate (HBrO ｘ ) or bromate hydrolysate (HBr, H ２ O, O ２) may be generated. Without exposing the substrate W to plasma, halogen HR may be removed by exposing the substrate W to a treatment gas. In this case, step ST2 may be performed in the chamber 10a of Figure 4. Alternatively, halogen HR may be removed by exposing the substrate W to a treatment gas without generating plasma. If the substrate W is not exposed to plasma, damage to the etching target film EL by plasma (e.g., change in film quality or reduction in the thickness direction of the film) can be suppressed. Alternatively, halogen HR may be removed by exposing the substrate W to plasma generated from the treatment gas. In this case, step ST2 may be performed in the plasma processing chamber 10 of Figure 3. After removing halogen HR, additional heating may be performed on the substrate W. This may cause dehydration condensation between the hydroxyl groups that have been replaced by halogen HR on the substrate W, promoting a crosslinking reaction. As a result, the film quality of the metal-containing mask MK may be improved.

[0050] The treatment gas is an oxygen-containing gas, an amine gas, and ammonia (NH4). ３ The oxygen-containing gas may contain at least one gas selected from the group consisting of gases. The oxygen-containing gas may contain an oxidizing agent. The oxygen-containing gas is H ２ O gas, hydrogen peroxide (H ２ O ２ ) gas, alcohol gas and ozone (O ３ It may contain at least one selected from the group consisting of ) gases. Hydrogen peroxide gas may be produced by vaporizing hydrogen peroxide solution (an aqueous solution containing hydrogen peroxide) using a vaporizer. The amount of hydrogen peroxide in the hydrogen peroxide solution may be 5% by mass or more, 8% by mass or more, or 10% by mass or more. Alternatively, the amount of hydrogen peroxide in the hydrogen peroxide solution may be 40% by mass or less, 38% by mass or less, or 36% by mass or less. In one example, the amount of hydrogen peroxide in the hydrogen peroxide solution may be 10% by mass or more and 36% by mass or less. The alcohol gas is methanol (CH4). ３ Oxygen-containing gas may also be oxygen (O). ２The gas may be an oxygen-containing gas other than the specified gas. The amine gas may include at least one selected from the group consisting of dimethylamine gas and trimethylamine. The treatment gas may further include a noble gas such as argon (Ar) gas.

[0051] In step ST2, the temperature of the substrate support portion 11 may be 300°C or less, 200°C or less, less than 160°C, 100°C or less, or 80°C or less. In step ST2, the temperature of the substrate support portion 11 may be 0°C or higher, 25°C or higher, 40°C or higher, or 100°C or higher. In step ST2, the temperature of the substrate support portion 11 may be above the melting point of the gas contained in the treatment gas.

[0052] In step ST2, the pressure inside the chamber 10a or the plasma processing chamber 10 may be 100 kPa (750 Torr) or less, 13.3 Pa (100 mTorr) or more, 66.7 Pa (500 mTorr) or more, 133 Pa (1 Torr) or more, 1.33 kPa (10 Torr) or more, or 13.3 kPa (100 Torr) or more.

[0053] The processing time for process ST2 may be 15 seconds or more, 30 seconds or more, or 1 minute or more. The processing time for process ST2 may be 10 minutes or less, or less than 1 minute.

[0054] Since halogen HR can be removed in step ST2, the substrate W does not need to be baked between step ST13 and step ST2.

[0055] As mentioned above, step ST2 may be performed simultaneously with step ST14. In this case, the plasma generated from the mixed gas containing the processing gas and the treatment gas removes scum from the surface of the metal-containing mask MK and the surface of the etched film EL, and also removes halogen HR.

[0056] (Process ST3) In process ST3, the surface of the substrate W (e.g., dimensions, roughness, defects) is inspected using an ADI device.

[0057] (Step ST4) In step ST4, as shown in Figure 9, the substrate W is exposed to plasma PL generated from the etching gas to etch the film EL to be etched. As a result, recesses RS corresponding to the opening OP of the metal-containing mask MK are formed in the film EL to be etched. The bottom of the recesses RS may reach the substrate region UR. The etching gas may be different from the treatment gas in step ST2. The etching gas is oxygen (O ２ ) gas or nitrogen (N ２ ) May contain gas.

[0058] Processes ST13, ST2, and ST4 may be carried out in different chambers. For example, in the substrate processing apparatus SPA of Figure 1, process ST13 may be carried out in process module P1, process ST2 in process module P3, and process ST4 in process module P2.

[0059] At least two of steps ST13, ST2, and ST4 may be performed in the same chamber. For example, in the substrate processing apparatus SPA of Figure 1, steps ST13 and ST4 may be performed in process module P1, and step ST2 may be performed in process module P3. Steps ST13, ST2, and ST4 may be performed in the same chamber. For example, in the plasma processing apparatus 1 of Figures 2 and 3, steps ST13, ST2, and ST4 may be performed.

[0060] According to the substrate processing apparatus SPA and method MT1 described above, halogen HR shown in Figure 7 can be removed. This also suppresses contamination (e.g., contamination of other substrates or equipment) due to the release of halogen HR from the substrate W after the completion of method MT1. Furthermore, the etching resistance of the metal-containing mask MK in step ST4 can be improved. As a result, the enlargement of the dimensions (CD) of the recess RS formed by step ST4 can be suppressed, and the edge roughness and defects (e.g., pinching defects) of the recess RS can also be reduced. By performing step ST2, halogen HR can be removed at low temperature, low pressure, and in a short time.

[0061] The amount of halogen HR removed can be adjusted by adjusting the temperature of the substrate support section 11 and the pressure inside the chamber 10a or the plasma treatment chamber 10, depending on the type of gas contained in the treatment gas.

[0062] The following describes various experiments conducted to evaluate Method MT1. The experiments described below are not intended to limit this disclosure.

[0063] (First Experiment) In the first experiment, a substrate having the same structure as substrate W shown in Figure 6 was prepared (step ST11). The substrate comprises a silicon substrate, a spin-on carbon (SOC) film on the silicon substrate, a SiOC film on the SOC film, and a tin-containing resist on the SiOC film. The tin-containing resist has an exposed region and an unexposed region.

[0064] Next, the substrate was exposed to a developing gas containing hydrogen bromide (HBr) to develop the tin-containing resist (step ST13). The development formed a tin-containing resist mask with openings.

[0065] Next, argon (Ar) gas and H ２ The substrate was exposed to a treatment gas containing O gas (step ST2). The temperature of the substrate support was 250°C. The pressure inside the chamber was 13.3 kPa (100 Torr). H gas relative to the partial pressure of argon gas. ２ The ratio of the partial pressures of gas O is 1. The substrate was exposed to the treatment gas for 10 minutes.

[0066] (Second experiment) In process ST2, H２ Methanol (CH) can be used instead of O gas. ３ The experiment was conducted in the same manner as the first experiment, except that OH) gas was used.

[0067] (Third experiment) In process ST2, H ２ Ammonia (NH) instead of O gas ３ The experiment was conducted in the same manner as the first experiment, except that gas was used.

[0068] (Fourth experiment) In process ST2, H ２ The experiment was conducted in the same manner as the first experiment, except that dimethylamine gas was used instead of oxygen gas.

[0069] (Experiment 5) In step ST2, H ２ Oxygen (O) instead of O gas ２ The experiment was conducted in the same manner as the first experiment, except that gas was used.

[0070] (Experiment 6) In step ST2, H ２ The experiment was conducted in the same manner as the first experiment, except that O gas was not used. That is, in step ST2, the substrate was exposed to argon gas only.

[0071] (Evaluation Results of Bromine Atom Concentration) The surface of the tin-containing resist masks obtained in Experiments 1 to 6 was analyzed by X-ray photoelectron spectroscopy (XPS). For Experiments 1 to 6, the concentration (%) of bromine atoms (Br) relative to tin atoms (Sn) was calculated. The results are shown in Figure 10. In Figure 10, Ar represents the result for Experiment 6. ２ This shows the results of the fifth experiment. H ２ O indicates the results of the first experiment. MeOH indicates the results of the second experiment. NH ３ The results of the third experiment are shown. DMA shows the results of the fourth experiment.

[0072] As shown in Figure 10, it can be seen that bromine is removed when a treatment gas is used. This indicates that bromine remaining on the tin-containing resist mask reacts with the treatment gas and volatilizes as a bromine compound. When the treatment gas contains an oxygen-containing gas, substances containing Sn-Br bonds are oxidized, and bromine is converted into bromate (HBrO). ｘ) or volatilizes as a decomposition product thereof, SnO ｘ Alternatively, it is thought that SnOH is produced. If the treatment gas contains ammonia gas or amine gas, it is thought that volatile bromide salts are produced by the reaction of a substance containing a Sn-Br bond with the treatment gas.

[0073] (Experiment 7) The experiment was conducted in the same manner as in Experiment 1, except that the temperature of the substrate support part was set to 100°C in step ST2. The treatment gas was Ar gas and H ２ It contains O gas.

[0074] (Experiment 8) The experiment was conducted in the same manner as in Experiment 2, except that the temperature of the substrate support part was set to 100°C in step ST2. The treatment gases were Ar gas and CH ３ Contains OH gas.

[0075] (Experiment 9) The experiment was conducted in the same manner as in Experiment 3, except that the temperature of the substrate support part was set to 100°C in step ST2. The treatment gases were Ar gas and NH ３ Includes gas.

[0076] (Experiment 10) The experiment was carried out in the same manner as in Experiment 4, except that the temperature of the substrate support part was set to 100°C in step ST2. The treatment gas contained Ar gas and dimethylamine gas.

[0077] (Experiment 11) The experiment was conducted in the same manner as in Experiment 5, except that the temperature of the substrate support part was set to 100°C in step ST2. The treatment gas was Ar gas and O ２ Includes gas.

[0078] (Experiment 12) The experiment was conducted in the same manner as in Experiment 6, except that the temperature of the substrate support part was set to 100°C in step ST2.

[0079] (Experiment 13) In step ST2, H ２ Replace O gas with 35% hydrogen peroxide (H ２ O ２ The experiment was conducted in the same manner as in Experiment 7, except that gas was used. 35% H ２ O ２The gas was obtained by vaporizing 35% hydrogen peroxide solution using a vaporizer. "35% H" ２ O ２ gas" contains H ２ O gas and H ２ O ２ gas. The gas ratio is H ２ O gas : H ２ O ２ gas = 0.65:0.35.

[0080] (Experiment 14) In step ST2, an experiment was conducted in the same manner as in Experiment 7, except that ozone (O ２ ３ ２ ) gas was used instead of H

[0081] (Evaluation results of temperature dependence) The surface of the tin-containing resist mask on the substrate obtained in Experiments 7 to 14 was analyzed by X-ray photoelectron spectroscopy (XPS). For Experiments 7 to 14, the concentration (%) of bromine atoms (Br) with respect to tin atoms (Sn) was calculated. The results are shown in Fig. 11. In Fig. 11, Ar shows the results of Experiment 12. O ２ shows the results of Experiment 11. H ２ O shows the results of Experiment 7. MeOH shows the results of Experiment 8. NH ３ shows the results of Experiment 9. DMA shows the results of Experiment 10. H<s ２ [[ID=]34]O ２ shows the results of Experiment 13. O ３ shows the results of Experiment 14.

[0082] As shown in Fig. 11, it can be seen that at low temperatures, the amount of bromine removed can be increased by using H ２ O ２ gas or O ３ gas.

[0083] (Experiment 15) In step ST2, an experiment was conducted in the same manner as in Experiment 13, except that the pressure in the chamber was set to 1.33 kPa (10 Torr).

[0084] (Experiment 16) In step ST2, an experiment was conducted in the same manner as in Experiment 14, except that the pressure in the chamber was set to 1.33 kPa (10 Torr).

[0085] (Evaluation Results of Pressure Dependence) The surface of the tin-containing resist mask on the substrate obtained in the 15th to 16th experiments was analyzed by X-ray photoelectron spectroscopy (XPS), and the concentration (%) of bromine atoms (Br) relative to tin atoms (Sn) was calculated. The bromine atom concentration (%) in the 15th experiment was approximately one-tenth of the bromine atom concentration (%) before step ST2 and was equivalent to the bromine atom concentration in the 13th experiment. On the other hand, the bromine atom concentration (%) in the 16th experiment was approximately one-half of the bromine atom concentration before step ST2 and was greater than the bromine atom concentration (%) in the 14th experiment. Therefore, it can be seen that when using H ２ O ２ gas, the amount of bromine removed does not decrease even at low pressures compared to O ３ gas.

[0086] (Evaluation Results of Film Quality) The cross-sections of the substrates obtained in the 13th to 16th experiments were observed to evaluate the film quality of the SOC film and the SiO C film. In the 13th and 14th experiments, no change was observed in the film quality of the SOC film and the SiO C film. On the other hand, in the 15th and 16th experiments, it was confirmed that the SOC film was shrinking in the thickness direction and the SOC film was deteriorated. Therefore, it can be seen that when using H ２ O ２ gas, damage to the carbon-containing film can be suppressed compared to O ３ gas.

[0087] (17th Experiment) An experiment was conducted in the same manner as the 1st experiment except that step ST2 was performed as follows. In step ST2, the substrate was exposed to a treatment gas containing argon (Ar) gas and 35% H ２ O ２ gas. The 35% H ２ O ２ gas was obtained by vaporizing 35 mass% hydrogen peroxide water with a vaporizer. The temperature of the substrate support part is 100°C. The pressure inside the chamber is 1.33 kPa (10 Torr). The ratio of the partial pressure of H ２ O ２ gas to the partial pressure of argon gas is 0.35. The time for exposing the substrate to the treatment gas is 60 seconds, 300 seconds, or 600 seconds.

[0088] (Experiment 18) The experiment was conducted in the same manner as in Experiment 17, except that the pressure inside the chamber was set to 0.67 kPa (5 Torr) in step ST2.

[0089] (Experiment 19) The experiment was conducted in the same manner as in Experiment 17, except that the pressure inside the chamber was set to 0.13 kPa (1 Torr) in step ST2.

[0090] (Pressure and Time Dependence Evaluation Results) The surface of the tin-containing resist masks obtained in Experiments 17 to 19 was analyzed by X-ray photoelectron spectroscopy (XPS). For Experiments 17 to 19, the concentration (%) of bromine atoms (Br) relative to tin atoms (Sn) was calculated. The results are shown in Figure 12. In Figure 12, EX17 shows the results of Experiment 17. EX18 shows the results of Experiment 18. EX19 shows the results of Experiment 19.

[0091] As shown in Figure 12, it can be seen that the amount of bromine removed does not decrease even when the pressure inside the chamber is reduced. Furthermore, it can be seen that bromine can be sufficiently removed even with a treatment gas treatment time of 60 seconds.

[0092] (Experiment 20) A substrate having a tin-containing resist with residual chlorine was prepared (Step ST1). Next, 35% hydrogen peroxide (H ２ O ２ The substrate was exposed to a treatment gas containing ) gas (step ST2). The temperature of the substrate support was 100°C. The pressure inside the chamber was 13.3 kPa (100 Torr). H in relation to the partial pressure of argon gas ２ O ２ The ratio of the partial pressures of the gases is 0.35. The substrate was exposed to the treatment gas for 10 minutes.

[0093] (Experiment 21) The experiment was conducted in the same manner as in Experiment 20, except that a substrate with a tin-containing resist containing residual fluorine was prepared in step ST1.

[0094] (Experiment 22) The experiment was conducted in the same manner as in Experiment 20, except that the pressure inside the chamber was set to 1.33 kPa (10 Torr) in step ST2.

[0095] (Experiment 23) The experiment was conducted in the same manner as in Experiment 21, except that the pressure inside the chamber was set to 1.33 kPa (10 Torr) in step ST2.

[0096] (24th experiment) In step ST2, H ２ The experiment was conducted in the same manner as in Experiment 20, except that a treatment gas containing O gas was used.

[0097] (25th experiment) In step ST2, H ２ The experiment was conducted in the same manner as in Experiment 21, except that a treatment gas containing O gas was used.

[0098] (Experiment 26) In step ST2, methanol (CH ３ The experiment was conducted in the same manner as in Experiment 20, except that a treatment gas containing OH) gas was used.

[0099] (Experiment 27) In step ST2, methanol (CH ３ The experiment was conducted in the same manner as in Experiment 21, except that a treatment gas containing OH) gas was used.

[0100] (Experiment 28) The experiment was conducted in the same manner as in Experiment 20, except that a treatment gas containing dimethylamine gas was used in step ST2.

[0101] (Experiment 29) The experiment was conducted in the same manner as in Experiment 21, except that a treatment gas containing dimethylamine gas was used in step ST2.

[0102] (Experiment 30) In step ST2, methanol (CH ３ The experiment was conducted in the same manner as in Experiment 22, except that a treatment gas containing OH) gas was used.

[0103] (Experiment 31) In step ST2, methanol (CH ３ The experiment was conducted in the same manner as in Experiment 23, except that a treatment gas containing OH) gas was used.

[0104] (Experiment 32) The experiment was conducted in the same manner as in Experiment 22, except that the temperature of the substrate support part was set to 250°C in step ST2.

[0105] (Experiment 33) The experiment was conducted in the same manner as in Experiment 23, except that the temperature of the substrate support part was set to 250°C in step ST2.

[0106] (Experiment 34) In step ST2, H ２ The experiment was conducted in the same manner as in Experiment 22, except that a treatment gas containing O gas was used and the temperature of the substrate support was set to 250°C.

[0107] (Experiment 35) In step ST2, H ２ The experiment was conducted in the same manner as in Experiment 23, except that a treatment gas containing O gas was used and the temperature of the substrate support was set to 250°C.

[0108] (Experiment 36) In step ST2, oxygen (O ２ The experiment was conducted in the same manner as in Experiment 22, except that a treatment gas containing the gas was used and the temperature of the substrate support was set to 250°C.

[0109] (Experiment 37) In step ST2, oxygen (O ２ The experiment was conducted in the same manner as in Experiment 23, except that a treatment gas containing the gas was used and the temperature of the substrate support was set to 250°C.

[0110] (Experiment 38) In step ST2, methanol (CH ３ The experiment was conducted in the same manner as in Experiment 22, except that a treatment gas containing OH) gas was used and the temperature of the substrate support was set to 250°C.

[0111] (Experiment 39) In step ST2, methanol (CH ３ The experiment was conducted in the same manner as in Experiment 23, except that a treatment gas containing OH) gas was used and the temperature of the substrate support was set to 250°C.

[0112] (Experiment 40) The experiment was conducted in the same manner as in Experiment 22, except that a treatment gas containing dimethylamine gas was used in step ST2 and the temperature of the substrate support was set to 250°C.

[0113] (Experiment 41) The experiment was conducted in the same manner as in Experiment 23, except that a treatment gas containing dimethylamine gas was used in step ST2 and the temperature of the substrate support was set to 250°C.

[0114] (Evaluation results of halogen atom concentration) The surface of the tin-containing resist masks of the substrates obtained in Experiments 20 to 41 was analyzed by X-ray photoelectron spectroscopy (XPS). The surface of the tin-containing resist mask was also analyzed by XPS before process ST2. For Experiments 20 to 41, the concentration (%) of halogen atoms relative to tin atoms (Sn) was calculated. As a result, in Experiments 20 to 41, the halogen atom concentration after process ST2 was lower than the halogen atom concentration before process ST2. Higher pressure in the chamber increased the amount of halogen removed. Higher temperature of the substrate support increased the amount of halogen removed.

[0115] (Experiment 42) In Experiment 42, a substrate having the same structure as substrate W shown in Figure 6 was prepared (Step ST11). The substrate comprises a silicon substrate, a film to be etched on the silicon substrate, and a tin-containing resist on the film to be etched. The tin-containing resist has an exposed region and an unexposed region.

[0116] Next, the substrate was exposed to a developing gas containing hydrogen bromide (HBr) to develop the tin-containing resist (step ST13). The development formed a tin-containing resist mask with openings.

[0117] Next, without generating plasma, 35% H ２ O ２ The substrate was exposed to a treatment gas containing gas (step ST2). 35%H ２ O ２ The gas was obtained by vaporizing 35% by mass hydrogen peroxide solution using a vaporizer. The temperature of the substrate support was 150°C. The pressure inside the chamber was 933 Pa (7 Torr). The substrate was exposed to the treatment gas for 5 minutes. Steps ST13 and ST2 were performed in-system.

[0118] (Experiment 43) In step ST2, 35% H ２ O２ Nitrogen (N) instead of gas ２ The experiment was conducted in the same manner as in Experiment 42, except that gas was used.

[0119] (Experiment 44) The experiment was conducted in the same manner as Experiment 42, except that step ST2 was not performed.

[0120] (Contamination Evaluation Results) A bare silicon wafer was placed on the shelf one level above the bottom shelf of the FOSB (Front Opening Shipping Box). Subsequently, the substrates obtained in Experiments 42 to 44 were placed on the bottom shelf of the FOSB. The tin-containing resist mask of the substrate was facing the back surface of the bare silicon wafer. After 48 hours, the bare silicon wafer was removed, and the back surface of the bare silicon wafer was analyzed by ICP-MS (Inductively Coupled Plasma Mass Spectrometry). As a result, in Experiment 42, the tin concentration was 4.97 × 10⁻⁶. ９ atoms / cm ２ In the 43rd experiment, the tin concentration was 1.17 × 10⁻⁶. １２ atoms / cm ２ In the 44th experiment, the tin concentration was 1.77 × 10⁻⁶. １２ atoms / cm ２ In Experiment 42, the tin concentration (number of atoms per square meter) was less than 1 / 200th of that in Experiments 43 and 44. In Experiment 43, the tin concentration had decreased slightly. This is thought to be due to the heating of the substrate. H ２ O ２ Exposure of the substrate to a treatment gas containing gas suggested a significant reduction in tin emissions from the substrate.

[0121] In Experiment 42, the concentration of bromine atoms was less than 1 / 50th of that in Experiments 43 and 44. ２ O ２ It was suggested that bromine atoms can be removed from the entire surface of the substrate by exposing it to a treatment gas containing gas.

[0122] (Experiment 45) The experiment was conducted in the same manner as in Experiment 42, except that in step ST2, the temperature of the substrate support was set to 80°C, the pressure inside the chamber to 133 Pa (1 Torr), and the time the substrate was exposed to the treatment gas was 90 seconds.

[0123] (Experiment 46) The experiment was conducted in the same manner as in Experiment 45, except that the temperature of the substrate support part was set to 60°C in step ST2.

[0124] (Experiment 47) The experiment was conducted in the same manner as in Experiment 45, except that the temperature of the substrate support part was set to 40°C in step ST2.

[0125] (48th experiment) In step ST2, 35% H ２ O ２ N instead of gas ２ The experiment was conducted in the same manner as Experiment 45, except that gas was used.

[0126] (49th experiment) In step ST2, 35% H ２ O ２ N instead of gas ２ The experiment was conducted in the same manner as Experiment 46, except that gas was used.

[0127] (Experiment 50) In step ST2, 35% H ２ O ２ N instead of gas ２ The experiment was conducted in the same manner as Experiment 47, except that gas was used.

[0128] (Temperature-dependent evaluation results) The surface of the tin-containing resist masks obtained in Experiments 42 to 50 was analyzed by X-ray photoelectron spectroscopy (XPS). For Experiments 42 to 50, the concentration (%) of bromine atoms (Br) relative to tin atoms (Sn) was calculated. As a result, Experiments 42 and 45 to 47 (H ２ O ２ Gas) was used in Experiment 43 and Experiments 48 to 50 (N ２ Compared to Experiment 44 (without treatment gas), the concentration of bromine atoms was less than one-sixth. Even at low temperatures in the substrate support area, H ２ O ２It was suggested that bromine atoms can be removed from a substrate by exposing it to a treatment gas containing gas.

[0129] (Experiment 51) The experiment was conducted in the same manner as in Experiment 42, except that the pressure inside the chamber was set to 533 Pa (4 Torr) in step ST2.

[0130] (Experiment 52) ​​The experiment was conducted in the same manner as in Experiment 42, except that the pressure inside the chamber was set to 133 Pa (1 Torr) in step ST2.

[0131] (Experiment 53) In step ST2, 35% H ２ O ２ N instead of gas ２ The experiment was conducted in the same manner as Experiment 51, except that gas was used.

[0132] (Experiment 54) In step ST2, 35% H ２ O ２ N instead of gas ２ The experiment was conducted in the same manner as Experiment 52, except that gas was used.

[0133] (Evaluation results of pressure dependence) The surface of the tin-containing resist masks on the substrates obtained in Experiments 42-43 and 51-54 was analyzed by X-ray photoelectron spectroscopy (XPS). The concentration (%) of bromine atoms (Br) relative to tin atoms (Sn) was calculated. As a result, in Experiments 42 and 51-52 (H ２ O ２ Gas) was used in Experiment 43 and Experiments 53-54 (N ２ Compared to Experiment 44 (without treatment gas), the concentration of bromine atoms was about 1 / 50th. Even at low pressure in the chamber, H ２ O ２ It was suggested that bromine atoms can be removed from a substrate by exposing it to a treatment gas containing gas.

[0134] (Experiment 55) The experiment was conducted in the same manner as in Experiment 42, except that the time the substrate was exposed to the treatment gas in step ST2 was set to 90 seconds.

[0135] (Experiment 56) In step ST2, 35% H was used as the treatment gas. ２ O ２ Gas and N ２ The experiment was conducted in the same manner as in Experiment 55, except that a mixed gas containing gas and at a flow rate ratio of 1:1 was used. ２ H to gas ２ O ２ The ratio of the partial pressures of the gases is 0.35.

[0136] (Experiment 57) In step ST2, 35% H was used as the treatment gas. ２ O ２ Gas and N ２ The experiment was conducted in the same manner as in Experiment 55, except that a mixed gas containing gas and at a flow rate ratio of 1:3 was used. ２ H to gas ２ O ２ The ratio of the partial pressures of the gases is 0.12.

[0137] (Experiment 58) In step ST2, 35% H ２ O ２ N instead of gas ２ The experiment was conducted in the same manner as Experiment 55, except that gas was used.

[0138] (Experiment 59) The experiment was conducted in the same manner as in Experiment 55, except that the pressure inside the chamber was set to 133 Pa (1 Torr) in step ST2.

[0139] (Experiment 60) The experiment was conducted in the same manner as in Experiment 56, except that the pressure inside the chamber was set to 133 Pa (1 Torr) in step ST2.

[0140] (Experiment 61) The experiment was conducted in the same manner as in Experiment 57, except that the pressure inside the chamber was set to 133 Pa (1 Torr) in step ST2.

[0141] (Experiment 62) The experiment was conducted in the same manner as in Experiment 58, except that the pressure inside the chamber was set to 133 Pa (1 Torr) in step ST2.

[0142] (Experiment 63) The experiment was conducted in the same manner as in Experiment 55, except that the temperature of the substrate support part was set to 60°C in step ST2.

[0143] (Experiment 64) The experiment was conducted in the same manner as in Experiment 56, except that the temperature of the substrate support part was set to 60°C in step ST2.

[0144] (Experiment 65) The experiment was conducted in the same manner as in Experiment 57, except that the temperature of the substrate support part was set to 60°C in step ST2.

[0145] (Experiment 66) The experiment was conducted in the same manner as in Experiment 58, except that the temperature of the substrate support part was set to 60°C in step ST2.

[0146] (Experiment 67) The experiment was conducted in the same manner as in Experiment 55, except that in step ST2, the pressure inside the chamber was set to 133 Pa (1 Torr) and the temperature of the substrate support was set to 60°C.

[0147] (Experiment 68) The experiment was conducted in the same manner as in Experiment 56, except that in step ST2, the pressure inside the chamber was set to 133 Pa (1 Torr) and the temperature of the substrate support part was set to 60°C.

[0148] (Experiment 69) The experiment was conducted in the same manner as in Experiment 57, except that in step ST2, the pressure inside the chamber was set to 133 Pa (1 Torr) and the temperature of the substrate support was set to 60°C.

[0149] (Experiment 70) The experiment was conducted in the same manner as in Experiment 58, except that in step ST2, the pressure inside the chamber was set to 133 Pa (1 Torr) and the temperature of the substrate support was set to 60°C.

[0150] (Evaluation results of partial pressure dependence) The surface of the tin-containing resist masks of the substrates obtained in Experiment 44 and Experiments 55 to 70 was analyzed by X-ray photoelectron spectroscopy (XPS). For Experiments 44 and Experiments 55 to 77, the concentration (%) of bromine atoms (Br) relative to tin atoms (Sn) was calculated. The results are shown in Figure 13. In Figure 13, EX55 to EX70 show the results of Experiments 55 to 70, respectively. EX44 shows the result of Experiment 44.

[0151] As shown in Figure 13, N ２ H to gas ２ O ２It can be seen that even when the ratio of gas partial pressures is 0.35 (Ex56, EX60, and EX68), the amount of bromine removed does not decrease significantly. ２ H to gas ２ O ２ It can be seen that bromine can be removed even when the ratio of gas partial pressures is 0.12 (EX57, EX61, EX65, and EX69). It can also be seen that increasing at least one of the following—the pressure inside the chamber or the temperature of the substrate support—increases the amount of bromine removed.

[0152] (Experiment 71) The experiment was conducted in the same manner as in Experiment 42, except that the time the substrate was exposed to the treatment gas in step ST2 was set to 30 seconds, 90 seconds, 60 seconds, or 300 seconds.

[0153] (Experiment 72) The experiment was conducted in the same manner as in Experiment 71, except that the temperature of the substrate support part was set to 60°C in step ST2.

[0154] (Experiment 73) The experiment was conducted in the same manner as in Experiment 42, except that in step ST2, the pressure inside the chamber was set to 133 Pa (1 Torr), the temperature of the substrate support was set to 60°C, and the time the substrate was exposed to the treatment gas was set to 30 seconds or 90 seconds.

[0155] (Evaluation results dependent on temperature, pressure, and time) The surface of the tin-containing resist masks of the substrates obtained in Experiments 71 to 73 was analyzed by X-ray photoelectron spectroscopy (XPS). For Experiments 71 to 73, the concentration (%) of bromine atoms (Br) relative to tin atoms (Sn) was calculated. The results are shown in Figure 14. In Figure 14, EX71 shows the results of Experiment 71. EX72 shows the results of Experiment 72. EX73 shows the results of Experiment 73.

[0156] As shown in Figure 14, it can be seen that lowering the temperature of the substrate support does not reduce the amount of bromine removed. Furthermore, it can be seen that bromine can be sufficiently removed even when the pressure inside the chamber is lowered. In addition, it can be seen that bromine can be sufficiently removed even when the exposure time of the substrate to the treatment gas is shortened.

[0157] (Experiment 74) The experiment was conducted in the same manner as in Experiment 42, except that the time the substrate was exposed to the treatment gas in step ST2 was set to 30 seconds or 90 seconds.

[0158] (Experiment 75) The experiment was conducted in the same manner as in Experiment 74, except that a baking process was performed between the developing process (step ST13) and the treatment gas process (step ST2).

[0159] (Evaluation of the effects of baking) The surface of the tin-containing resist masks of the substrates obtained in Experiment 74 and Experiment 75 was analyzed by X-ray photoelectron spectroscopy (XPS). For Experiments 74 and 75, the concentration (%) of bromine atoms (Br) relative to tin atoms (Sn) was calculated. The results are shown in Figure 15. In Figure 15, EX74 shows the results of Experiment 74. EX75 shows the results of Experiment 75.

[0160] As shown in Figure 15, the amount of bromine removed by the treatment gas was almost the same regardless of whether a baking step was performed or not. Therefore, it can be seen that bromine can be sufficiently removed even without performing a baking step between the developing step (step ST13) and the treatment gas treatment step (step ST2).

[0161] (Experiment 76) The experiment was conducted in the same manner as in Experiment 74, except that the temperature of the substrate support part was set to 60°C in step ST2.

[0162] (Experiment 77) The experiment was conducted in the same manner as in Experiment 76, except that a baking process was performed between the developing process (step ST13) and the treatment gas process (step ST2).

[0163] (Evaluation of the effects of baking) The surface of the tin-containing resist masks of the substrates obtained in Experiment 76 and Experiment 77 was analyzed by X-ray photoelectron spectroscopy (XPS). For Experiments 76 and 77, the concentration (%) of bromine atoms (Br) relative to tin atoms (Sn) was calculated. The results are shown in Figure 16. In Figure 16, EX76 shows the results of Experiment 76. EX77 shows the results of Experiment 77.

[0164] As shown in Figure 16, the amount of bromine removed by the treatment gas was almost the same regardless of whether a bake step was performed or not. Therefore, it can be seen that bromine can be sufficiently removed even without performing a bake step between the developing step (step ST13) and the treatment gas treatment step (step ST2). Furthermore, it can be seen that bromine can be sufficiently removed even if the temperature of the substrate support part is low in step ST2.

[0165] (Experiment 78) The experiment was conducted in the same manner as in Experiment 42, except that a deathcam (step ST14) was performed between the development process (step ST13) and the treatment gas process (step ST2). The deathcam was performed by exposing the substrate W to plasma generated from a treatment gas containing halogen gas.

[0166] (Experiment 79) The experiment was conducted in the same manner as in Experiment 78, except that the temperature of the substrate support part was set to 60°C in step ST2.

[0167] (Experiment 80) In step ST2, N is used as the treatment gas. ２ The experiment was conducted in the same manner as Experiment 78, except that gas was used.

[0168] (Experiment 81) In step ST2, N is used as the treatment gas. ２ The experiment was conducted in the same manner as Experiment 79, except that gas was used.

[0169] (Experiment 82) The experiment was conducted in the same manner as Experiment 78, except that step ST2 was not performed.

[0170] (Evaluation of the effects of plasma treatment) The surface of the tin-containing resist masks of the substrates obtained in Experiments 78 to 82 was analyzed by X-ray photoelectron spectroscopy (XPS). For Experiments 78 to 82, the concentration (%) of bromine atoms (Br) relative to tin atoms (Sn) was calculated. The results are shown in Figure 17. In Figure 17, EX78 to EX82 show the results for Experiments 78 to 82, respectively. The vertical axis of Figure 17 shows the relative value of the Br atom concentration when the Br atom concentration of EX82 is set to 1.

[0171] As shown in Figure 17, even when a death cam is performed, H２ O ２ It can be seen that bromine can be sufficiently removed by treatment gas containing gas.

[0172] Figure 18 is a flowchart of a substrate processing method according to another exemplary embodiment. The substrate processing method MT2 shown in Figure 18 (hereinafter referred to as "method MT2") can be performed by the substrate processing apparatus SPA of Figure 1. Method MT2 can be applied to the substrate W1 of Figure 19. Method MT2 may be performed by the plasma processing apparatus 1 of Figures 2 and 3, or by the substrate processing apparatus 1a of Figure 4.

[0173] Figure 19 is a cross-sectional view of an example substrate to which the method of Figure 18 may be applied. As shown in Figure 19, in one embodiment, the substrate W1 comprises an etching target film EL and a metal-containing resist ML on the etching target film EL. The substrate W1 may further comprise a base region UR. The etching target film EL is positioned between the metal-containing resist ML and the base region UR. The substrate W1 may further comprise a film F1 between the base region UR and the etching target film EL. Film F1 may be an insulating film.

[0174] The etchable film EL may comprise films F2 to F6. Films F2 to F6 may be arranged sequentially from film F1 toward the metal-containing resist ML. Film F2 may be a metal-containing film containing titanium or tungsten (for example, a titanium nitride film or a tungsten-doped carbon film). Film F3 may be an oxide film such as a silicon oxide film. Film F4 may be a carbon-containing film. Film F5 may be an amorphous silicon film. Film F6 may be a carbon-containing film.

[0175] Hereinafter, Method MT2 will be described with reference to Figures 18 to 22, taking as an example the case in which Method MT2 is applied to the substrate W1 using the substrate processing apparatus SPA of the above embodiment. Figures 20 to 22 are cross-sectional views showing one step of a substrate processing method according to another exemplary embodiment. When the substrate processing apparatus SPA is used, Method MT2 can be executed in the substrate processing apparatus SPA by the control unit 2 controlling each part of the substrate processing apparatus SPA. In Method MT2, as shown in Figures 3 and 4, the substrate W1 on the substrate support unit 11 or mounting table 132 located in the plasma processing chamber 10 or chamber 10a may be processed.

[0176] As shown in Figure 18, Method MT2 may include steps ST1 to ST6. Steps ST1 to ST4 may be performed in the same way as in Method MT1. Step ST5 may be performed after step ST4. Step ST6 may be performed between steps ST2 and ST3. Method MT2 does not have to include at least one of steps ST2 or ST6, and may not include step ST6 at all. Step ST14 may be performed simultaneously with step ST2. Steps ST13, ST14, and ST2 may be performed in-situ or in-system. Step ST6 may be performed in-system with other steps or in a standalone chamber. If Method MT2 does not include step ST2, steps ST13 and ST14 may be performed in-situ.

[0177] By performing step ST1, a metal-containing mask MK is formed from the metal-containing resist ML, as shown in Figure 20.

[0178] (Step ST6) In step ST6, the substrate W1 is baked. The baking may be carried out in the same manner as in step ST12. The baking temperature may be 150°C or higher.

[0179] (Step ST4) In step ST4, as shown in Figure 21, the substrate W1 is exposed to plasma PL1 generated from the etching gas to etch the film EL to be etched. As a result, a metal-containing mask MK1 including at least one opening OP1 is formed on the film F1. The metal-containing mask MK and films F4 to F6 may be removed by etching. The metal-containing mask MK1 may include films F21 and F31 formed from films F2 and F3, respectively. The opening OP1 may have the same pattern as the opening OP of the metal-containing mask MK (see Figure 20).

[0180] The etching gas in step ST4 may contain halogens. In this case, halogen HR may remain on the substrate W1 after the completion of step ST4. Halogen HR may remain on the metal-containing mask MK1. Halogen HR may remain inside the metal-containing mask MK1. Halogen HR may be a compound containing a metal contained in the film EL to be etched and a halogen contained in the etching gas. If film F3 is an oxide film, the etching gas for film F3 may contain halogen-containing gases such as fluorocarbon gas. If film F2 is a metal-containing film, the etching gas for film F2 may contain halogen-containing gases such as chlorine gas.

[0181] (Step ST5) In step ST5, the substrate W1 is exposed to a treatment gas to remove halogen HR (see Figure 22). Step ST5 may be performed in the same way as step ST2. Steps ST4 and ST5 may be performed in-situ or in-system.

[0182] According to method MT2, halogen HR can be removed in step ST5. This prevents halogen HR remaining on the substrate W1 from forming metal salts in the atmosphere and becoming residue. Furthermore, it can suppress changes in the dimensions (CD) or shape of the opening OP1 of the metal-containing mask MK1. In addition, it can prevent excessive oxidation of the surface of the substrate W1 due to ashing with an oxygen-containing gas.

[0183] From the above description, it will be understood that the various embodiments of this disclosure are described herein for illustrative purposes and can be modified in various ways without departing from the scope and spirit of this disclosure. Accordingly, the various embodiments disclosed herein are not intended to limit the scope and spirit, and the true scope and spirit are shown by the appended claims.

[0184] Hereinafter, various exemplary embodiments included in this disclosure are described below.

[0185] [E1] A substrate processing method comprising: (a) a step of providing a substrate on a substrate support in a chamber, wherein the substrate comprises a film and a metal-containing mask on the film, the metal-containing mask includes at least one opening, and the substrate contains a halogen; and (b) a step of exposing the substrate to a treatment gas or plasma generated from the treatment gas to remove the halogen, wherein in (b), the temperature of the substrate support is less than 160°C.

[0186] [E2] The substrate processing method according to [E1], wherein, in (b), the substrate is exposed to the treatment gas without being exposed to the plasma.

[0187] [E3] The substrate treatment method according to [E1] or [E2], wherein the treatment gas comprises at least one gas selected from the group consisting of oxygen-containing gas, amine gas, and ammonia gas.

[0188] [E4] The oxygen-containing gas is H ２ The substrate processing method according to [E3], comprising at least one selected from the group consisting of O gas, hydrogen peroxide gas, alcohol gas, and ozone gas.

[0189] [E5] The substrate processing method according to [E3] or [E4], wherein the amine gas comprises dimethylamine gas.

[0190] [E6] The substrate processing method according to any one of [E1] to [E5], wherein the metal-containing mask comprises at least one metal selected from the group consisting of tungsten, molybdenum, titanium, tin, aluminum, zirconium, hafnium, indium, ruthenium, gallium, and zinc.

[0191] [E7] The substrate processing method according to any one of [E1] to [E6], wherein the film comprises a carbon-containing film.

[0192] [E8] The substrate processing method according to any one of [E1] to [E7], wherein in (b) above, the temperature of the substrate support portion is 80°C or less.

[0193] [E9] The substrate processing method according to any one of [E1] to [E8], wherein in (b) above, the pressure in the chamber is 100 kPa or less.

[0194] [E10] A substrate processing method according to any one of [E1] to [E9], wherein the substrate is a first substrate, and (a) comprises: (a1) a step of providing a second substrate comprising the film and a metal-containing resist on the film, wherein the metal-containing resist includes an exposed region and a non-exposed region; and (a2) a step of exposing the second substrate to a developing gas containing a halogen or a plasma generated from the developing gas to develop the metal-containing resist.

[0195] [E11] (c) A substrate processing method according to any one of [E1] to [E10], further comprising the step of exposing the substrate to plasma generated from an etching gas after (b) to etch the film.

[0196] [E12] The substrate processing method according to [E11], with reference to [E10], wherein (a2), (b), and (c) are performed in different chambers.

[0197] [E13] The substrate processing method according to [E11], referencing [E10], wherein at least two of (a2), (b), and (c) are performed in the same chamber.

[0198] [E14] The substrate processing method according to [E13], wherein (a2), (b), and (c) are performed in the same chamber.

[0199] [E15] A substrate processing method comprising: (a) a step of providing a substrate on a substrate support in a chamber, wherein the substrate comprises a film and a metal-containing mask on the film, the metal-containing mask includes at least one opening, and the substrate contains a halogen; (b) a step of performing a decam on the substrate; and (c) after (b), a step of exposing the substrate to a treatment gas or plasma generated from the treatment gas to remove the halogen.

[0200] [E16] A substrate processing method comprising: (a) a step of providing a substrate on a substrate support portion in a chamber, wherein the substrate comprises a film and a metal-containing resist on the film, the metal-containing resist including an exposed region and an unexposed region; (b) a step of exposing the substrate to a developing gas containing halogen or a plasma generated from the developing gas to develop the metal-containing resist; and (c) a step of exposing the substrate to a treatment gas or a plasma generated from the treatment gas to remove the halogen remaining on the substrate in (b).

[0201] [E17] The substrate processing method according to [E16], wherein the developing gas comprises at least one selected from the group consisting of hydrogen bromide, hydrogen fluoride, hydrogen chloride, boron trichloride, boron tribromide, boron trifluoride, chlorine, bromine, halomethane, halogen-containing carboxylic acid, and halogen-containing organic acid.

[0202] [E18] The substrate processing method according to [E16] or [E17], wherein, in (c), the substrate is exposed to the treatment gas without being exposed to the plasma.

[0203] [E19] The substrate treatment method according to any one of [E16] to [E18], wherein the treatment gas comprises at least one gas selected from the group consisting of oxygen-containing gas, amine gas, and ammonia gas.

[0204] [E20] A substrate processing apparatus comprising: a chamber; a substrate support portion for supporting a substrate within the chamber, wherein the substrate comprises a film and a metal-containing mask on the film, the metal-containing mask including at least one opening, and the substrate contains a halogen; a gas supply portion configured to supply a treatment gas to the chamber for removing the halogen; a temperature control mechanism configured to adjust the temperature of the substrate support portion; and a control unit configured to control the gas supply portion and the temperature control mechanism, wherein the control unit controls the gas supply portion and the temperature control mechanism to remove the halogen by exposing the substrate to the treatment gas while controlling the temperature of the substrate support portion to less than 160°C.

[0205] [E21] A substrate processing apparatus comprising: a chamber; a substrate support portion for supporting a substrate within the chamber, wherein the substrate comprises a film and a metal-containing mask on the film, the metal-containing mask including at least one opening, and the substrate contains a halogen; a gas supply unit configured to supply a treatment gas for removing the halogen and a processing gas into the chamber; a plasma generation unit configured to generate plasma from the processing gas; and a control unit configured to control the gas supply unit and the plasma generation unit, wherein the control unit controls the gas supply unit and the plasma generation unit to remove the halogen after performing a decam of the substrate with the plasma and then exposing the substrate to the treatment gas.

[0206] 1...Plasma processing apparatus, 2...Control unit, 10...Plasma processing chamber, 10a...Chamber, 11...Substrate support unit, 20...Gas supply unit, EL...Etching target film, HR...Halogen, MK...Metal-containing mask, ML...Metal-containing resist, OP...Aperture, SPA...Substrate processing apparatus, W...Substrate.

Claims

1. A substrate processing method comprising: (a) a step of providing a substrate on a substrate support in a chamber, wherein the substrate comprises a film and a metal-containing mask on the film, the metal-containing mask includes at least one opening, and the substrate contains a halogen; and (b) a step of exposing the substrate to a treatment gas or plasma generated from the treatment gas to remove the halogen, wherein in (b), the temperature of the substrate support is less than 160°C.

2. The substrate processing method according to claim 1, wherein, in (b) above, the substrate is exposed to the treatment gas without being exposed to the plasma.

3. The substrate treatment method according to claim 1 or 2, wherein the treatment gas comprises at least one gas selected from the group consisting of oxygen-containing gas, amine gas, and ammonia gas.

4. The oxygen-containing gas is H ２ The substrate processing method according to claim 3, comprising at least one selected from the group consisting of O gas, hydrogen peroxide gas, alcohol gas, and ozone gas.

5. The substrate processing method according to claim 3, wherein the amine gas includes dimethylamine gas.

6. The substrate processing method according to claim 1 or 2, wherein the metal-containing mask contains at least one metal selected from the group consisting of tungsten, molybdenum, titanium, tin, aluminum, zirconium, hafnium, indium, ruthenium, gallium, and zinc.

7. The substrate processing method according to claim 1 or 2, wherein the film includes a carbon-containing film.

8. The substrate processing method according to claim 1 or 2, wherein in (b) above, the temperature of the substrate support portion is 80°C or lower.

9. The substrate processing method according to claim 1 or 2, wherein, in (b) above, the pressure inside the chamber is 100 kPa or less.

10. The substrate processing method according to claim 1 or 2, wherein the substrate is a first substrate, and (a) comprises: (a1) a step of providing a second substrate comprising the film and a metal-containing resist on the film, wherein the metal-containing resist includes an exposed region and an unexposed region; and (a2) a step of exposing the second substrate to a developing gas containing a halogen or a plasma generated from the developing gas to develop the metal-containing resist.

11. (c) The substrate processing method according to claim 10, further comprising the step of exposing the substrate to plasma generated from an etching gas after (b) to etch the film.

12. The substrate processing method according to claim 11, wherein (a2), (b), and (c) are performed in different chambers.

13. The substrate processing method according to claim 11, wherein at least two of (a2), (b), and (c) are performed in the same chamber.

14. The substrate processing method according to claim 13, wherein (a2), (b), and (c) are performed in the same chamber.

15. A substrate processing method comprising: (a) providing a substrate on a substrate support in a chamber, wherein the substrate comprises a film and a metal-containing mask on the film, the metal-containing mask comprising at least one opening, and the substrate containing a halogen; (b) performing a decam on the substrate; and (c) after (b), exposing the substrate to a treatment gas or plasma generated from the treatment gas to remove the halogen.

16. A substrate processing method comprising: (a) providing a substrate on a substrate support in a chamber, wherein the substrate comprises a film and a metal-containing mask on the film, the metal-containing mask includes at least one opening, and the substrate contains halogen; and (b) exposing the substrate to a plasma generated from a mixed gas containing a treatment gas and a processing gas to decam the substrate and remove halogen from the substrate.

17. A substrate processing method comprising: (a) providing a substrate on a substrate support in a chamber, wherein the substrate comprises a film and a metal-containing mask on the film, the metal-containing mask comprising at least one opening, and the substrate containing a halogen; (b) exposing the substrate to a treatment gas or plasma generated from the treatment gas to remove the halogen; and baking the substrate at 150°C or higher before and / or after (b).

18. A substrate processing apparatus comprising: a chamber; a substrate support portion for supporting a substrate within the chamber, wherein the substrate comprises a film and a metal-containing mask on the film, the metal-containing mask including at least one opening, and the substrate contains a halogen; a gas supply unit configured to supply a treatment gas to the chamber for removing the halogen; a temperature control mechanism configured to adjust the temperature of the substrate support portion; and a control unit configured to control the gas supply unit and the temperature control mechanism, wherein the control unit controls the gas supply unit and the temperature control mechanism to remove the halogen by exposing the substrate to the treatment gas while controlling the temperature of the substrate support portion to less than 160°C.

19. A substrate processing apparatus comprising: a chamber; a substrate support portion for supporting a substrate within the chamber, wherein the substrate comprises a film and a metal-containing mask on the film, the metal-containing mask including at least one opening, and the substrate contains a halogen; a gas supply unit configured to supply a treatment gas for removing the halogen and a processing gas into the chamber; a plasma generation unit configured to generate plasma from the processing gas; and a control unit configured to control the gas supply unit and the plasma generation unit, wherein the control unit controls the gas supply unit and the plasma generation unit to remove the halogen after performing a decam of the substrate with the plasma and then exposing the substrate to the treatment gas.

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