Substrate treatment method

Abstract

To provide a substrate treatment method for forming a resist film which is thin and whose exposure part can be selectively eliminated.SOLUTION: A substrate treatment method includes the steps of: forming a laminate-structured film made by laminating a metal-containing layer and a halogen-containing layer on a substrate; irradiating the laminate-structured film with an extreme-ultraviolet ray in a predetermined pattern to form an exposed part irradiated with the extreme-ultraviolet ray and an unexposed part not irradiated with the extreme-ultraviolet ray, in the laminae-structured film; and selectively removing the exposed part of the laminate-structured film.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present disclosure relates to a method for processing a substrate. [Background technology]

[0002] Patent Document 1 discloses a pattern formation method including the steps of forming a photosensitive hard mask made of a transition metal oxide film on a surface of a substrate, exposing the photosensitive hard mask to EUV light in a desired pattern, causing a state change in an exposed region by heat generated during exposure, and selectively removing either the region in which the state change has occurred or the region in which the state change has not occurred. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2023-12048 A Summary of the Invention [Problem to be solved by the invention]

[0004] In one aspect, the present disclosure provides a substrate processing method for forming a resist film that is thin and capable of selectively removing an exposed portion. [Means for solving the problem]

[0005] In order to solve the above problem, according to one aspect, there is provided a substrate processing method comprising the steps of: forming a laminated structure film on a substrate, the laminated structure film being formed by stacking a metal-containing layer and a halogen-containing layer; irradiating the laminated structure film with extreme ultraviolet light in a predetermined pattern to form an exposed portion in the laminated structure film that is irradiated with the extreme ultraviolet light and an unexposed portion in the laminated structure film that is not irradiated with the extreme ultraviolet light; and selectively removing the exposed portion of the laminated structure film. Effect of the Invention

[0006] According to one aspect, the present disclosure can provide a substrate processing method for forming a resist film that is thin and allows selective removal of exposed portions. [Brief description of the drawings]

[0007] [Figure 1] 1 is a schematic cross-sectional view showing an example of a substrate processing apparatus according to an embodiment of the present invention; [Diagram 2] 4 is a flowchart showing an example of a substrate processing method according to the present embodiment. [Diagram 3] 1 is a schematic cross-sectional view of a substrate on which a resist film having an opening pattern is formed by the substrate processing method according to an embodiment of the present invention; [Figure 4] 1A and 1B are diagrams illustrating a structure of a resist film having a laminated structure formed by the substrate processing apparatus according to the present embodiment; [Diagram 5] 3A to 3C are diagrams illustrating the structure of a resist film in an exposed portion at each process. [Figure 6] 3A to 3C are diagrams illustrating the structure of an unexposed portion of a resist film at each process. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] Hereinafter, an embodiment of the present disclosure will be described with reference to the drawings. In the drawings, the same components are denoted by the same reference numerals, and duplicated descriptions may be omitted.

[0009] <Substrate processing equipment> An example of a substrate processing apparatus 1 according to this embodiment will be described with reference to Fig. 1. Fig. 1 is a schematic cross-sectional view showing an example of the substrate processing apparatus 1 according to this embodiment. The substrate processing apparatus 1 is a film forming apparatus that forms a laminated resist film (laminated structure film) 230 (see Fig. 3 described later) on a substrate W such as a semiconductor wafer by a chemical vapor deposition (CVD) method using plasma.

[0010] The substrate processing apparatus 1 includes a substantially cylindrical airtight processing vessel 2. An exhaust chamber 21 is provided in the center of the bottom wall of the processing vessel 2.

[0011] The exhaust chamber 21 has, for example, a substantially cylindrical shape that protrudes downward. An exhaust flow path 22 is connected to the exhaust chamber 21, for example, at a side surface of the exhaust chamber 21.

[0012] An exhaust unit 24 is connected to the exhaust flow path 22 via a pressure adjustment unit 23. The pressure adjustment unit 23 includes a pressure adjustment valve such as a butterfly valve. The exhaust flow path 22 is configured so that the inside of the processing vessel 2 can be depressurized by the exhaust unit 24. A transfer port 25 is provided on the side of the processing vessel 2. The transfer port 25 is configured so as to be freely opened and closed by a gate valve 26. The substrate W is loaded and unloaded between the inside of the processing vessel 2 and a transfer chamber (not shown) via the transfer port 25.

[0013] A mounting table 3 for holding the substrate W substantially horizontally is provided in the processing vessel 2. The mounting table 3 is formed in a substantially circular shape in a plan view, and is supported by a support member 31. A substantially circular recess 32 for mounting the substrate W having a diameter of, for example, 300 mm is formed on the surface of the mounting table 3. The recess 32 has an inner diameter that is slightly larger (for example, about 1 mm to 4 mm) than the diameter of the substrate W. The depth of the recess 32 is configured to be substantially the same as the thickness of the substrate W. The mounting table 3 is formed of a ceramic material such as aluminum nitride (AlN). The mounting table 3 may be formed of a metal material such as nickel (Ni). Instead of the recess 32, a guide ring for guiding the substrate W may be provided on the periphery of the surface of the mounting table 3.

[0014] A grounded lower electrode 33, for example, is embedded in the mounting table 3. A temperature adjustment mechanism 34 is embedded below the lower electrode 33. The temperature adjustment mechanism 34 adjusts the substrate W placed on the mounting table 3 to a set temperature based on a control signal from the control unit 9. If the mounting table 3 is entirely made of metal, the entire mounting table 3 functions as the lower electrode, so the lower electrode 33 does not need to be embedded in the mounting table 3. The mounting table 3 is provided with a plurality of (for example, three) lift pins 41 for holding and lifting the substrate W placed on the mounting table 3. The lift pins 41 are made of a material such as alumina (Al2 O 3 The lift pins 41 may be made of ceramics such as quartz or the like. The lower ends of the lift pins 41 are attached to a support plate 42. The support plate 42 is connected to a lift mechanism 44 provided outside the processing vessel 2 via a lift shaft 43.

[0015] The lifting mechanism 44 is installed, for example, at the bottom of the exhaust chamber 21. The bellows 45 is provided between the lifting mechanism 44 and an opening 211 for the lifting shaft 43 formed in the bottom surface of the exhaust chamber 21. The support plate 42 may be shaped so that it can be raised and lowered without interfering with the support member 31 of the mounting table 3. The lifting pins 41 are configured to be freely raised and lowered between the upper side and the lower side of the surface of the mounting table 3 by the lifting mechanism 44. In other words, the lifting pins 41 are configured to be able to protrude from the top surface of the mounting table 3.

[0016] A gas supply unit 5 is provided on the ceiling wall 27 of the processing vessel 2 via an insulating member 28. The gas supply unit 5 constitutes an upper electrode and faces the lower electrode 33. An RF power source 51 is connected to the gas supply unit 5 via a matching unit 511. The frequency band of the RF power source 51 is, for example, 450 kHz to 2.45 GHz. By supplying RF power from the RF power source 51 to the upper electrode (gas supply unit 5), an RF electric field is generated between the upper electrode (gas supply unit 5) and the lower electrode 33. The gas supply unit 5 includes a hollow gas diffusion chamber 52. A number of holes 53 for dispersing and supplying the processing gas into the processing vessel 2 are, for example, evenly arranged on the lower surface of the gas diffusion chamber 52. A heating mechanism 54 is embedded in the gas supply unit 5, for example, above the gas diffusion chamber 52. The heating mechanism 54 is heated to a set temperature by being supplied with power from a power source unit (not shown) based on a control signal from the control unit 9.

[0017] A gas supply path 6 is provided in the gas diffusion chamber 52. The gas supply path 6 is in communication with the gas diffusion chamber 52. A gas source 61 is connected to the upstream side of the gas supply path 6 via a gas line 62. The gas source 61 includes, for example, a supply source of various process gases, a mass flow controller, and a valve (none of which are shown). The various process gases include gases used in the above-mentioned method for forming a silicon-containing film. The various process gases are introduced from the gas source 61 through the gas line 62 into the gas diffusion chamber 52.

[0018] The various process gases include a first process gas containing a metal-containing precursor gas and a second process gas containing a halogen-containing precursor gas. The first process gas is a process gas used in forming a metal-containing layer 210 (see FIG. 3) in step S102 (see FIG. 2) described later. The second process gas is a process gas used in forming a halogen-containing layer 220 (see FIG. 3) in step S103 (see FIG. 2) described later. The first process gas and the second process gas will be described in detail later.

[0019] The substrate processing apparatus 1 includes a control unit 9. The control unit 9 is, for example, a computer, and includes a CPU (Central Processing Unit), a RAM (Random Access Memory), a ROM (Read Only Memory), an auxiliary storage device, etc. The CPU operates based on a program stored in the ROM or the auxiliary storage device, and controls the operation of the substrate processing apparatus 1. The control unit 9 may be provided inside or outside the substrate processing apparatus 1. When the control unit 9 is provided outside the substrate processing apparatus 1, the control unit 9 can control the substrate processing apparatus 1 by a communication means such as a wired or wireless communication means.

[0020] Although the substrate processing apparatus 1 has been described as a substrate processing apparatus that generates a capacitively coupled plasma (CCP), the present invention is not limited to this. The substrate processing apparatus may be a substrate processing apparatus that generates a remote plasma by radio frequency (RF, VHF) or microwave (MW). The substrate processing apparatus that generates a remote plasma may be a substrate processing apparatus that generates a remote plasma in a processing vessel that accommodates a substrate W, or a substrate processing apparatus that supplies the generated remote plasma into a processing vessel that accommodates a substrate W.

[0021] <Substrate processing method> Next, an example of a substrate processing method will be described with reference to Fig. 2 and Fig. 3(a) to Fig. 3(c). Fig. 2 is a flow chart showing an example of a substrate processing method according to this embodiment. Fig. 3(a) to Fig. 3(c) are examples of schematic cross-sectional views of a substrate W on which a resist film 230 having an opening pattern is formed by the substrate processing method according to this embodiment.

[0022] In step S101, a substrate W is prepared. Here, the substrate W to be prepared has an underlayer 200 (see FIG. 3(a)). The control unit 9 controls a transfer device (not shown) to transfer the substrate W having the underlayer 200 to the processing container 2 of the substrate processing apparatus 1 and place it in the recess 32 of the mounting table 3.

[0023] In step S102, a metal-containing layer 210 is formed on the substrate W. Here, the control unit 9 controls the gas source 61 to supply a first processing gas from the gas supply unit 5 into the processing chamber 2 through the multiple holes 53. The control unit 9 also controls the RF power supply 51 to supply RF power to the upper electrode (gas supply unit 5). This generates plasma of the first processing gas in the processing chamber 2, and the substrate W is exposed to the generated plasma to form the metal-containing layer 210 on the surface of the substrate W. The metal-containing layer 210 is preferably a metal-containing polymer layer. The metal-containing polymer layer contains metal (M), carbon (C), and hydrogen (H). The metal-containing polymer layer preferably contains a large amount of C-H bonds. The metal-containing polymer layer is formed at a low temperature to form a film containing a large amount of hydrogen (H), in other words, a film containing a large amount of C-H bonds.

[0024] Here, the first process gas includes a metal-containing precursor gas. The metal-containing precursor gas is a gas containing a metal (M) and hydrogen (H). Or, the metal-containing precursor gas is a gas containing a metal (M), carbon (C) and hydrogen (H). In other words, the metal-containing precursor gas is a gas represented by the chemical formula M X C Y H Z where M is a metal, X and Z are integers of 1 or more, and Y is 0 or an integer of 1 or more. Here, the metal (M) is one selected from Sn, Sb, In, Al, Ti, Mn, Ta, Hf, and W.

[0025] Specifically, the metal-containing precursor gas is Sn(CH 3 ) 4 , SnH(CH 3 ) 3 , SnH 2 (CH 3 ) 2 , Sn(C 2 H 5 ) 4 , Al(CH 3 ) 3 , Co(C 5 H 5 ) 2 , SnR 4 , SnHR 3 , (where R is -CH 3 , -C 2 H 3 , -C 3 H 5 , -C 4 H 7 , -C 6 H 6 ) is selected from.

[0026] The first process gas may also contain an additive gas and / or an inert gas. The additive gas may be H 2 , C 2 H 2 , HCl. The inert gas is He, Ar, Ne, Xr, N 2 At least one gas selected from the group consisting of:

[0027] An example of a recipe for the process of forming the metal-containing layer 210 is shown below. Plasma type: CCP, 13.56MHz, 10W~500W Mounting table temperature: 250℃ or less Pressure inside processing vessel: 100mTorr~20Torr

[0028] In step S103, a halogen-containing layer 220 is formed on the substrate W. Here, the control unit 9 controls the gas source 61 to supply a second processing gas from the gas supply unit 5 into the processing chamber 2 through a large number of holes 53. The control unit 9 also controls the RF power supply 51 to supply RF power to the upper electrode (gas supply unit 5). This generates plasma of the second processing gas in the processing chamber 2, and the substrate W is exposed to the generated plasma to form the halogen-containing layer 220 on the surface of the substrate W. The halogen-containing layer 220 is preferably a halogen-containing polymer layer. The halogen-containing polymer layer contains halogen (Ha), carbon (C), and hydrogen (H). The halogen-containing polymer layer is preferably one containing a large amount of C-H bonds. The halogen-containing polymer layer is formed at a low temperature to form a film containing a large amount of hydrogen (H), in other words, a film containing a large amount of C-H bonds.

[0029] Here, the second process gas includes a halogen-containing precursor gas. The halogen-containing precursor gas is a gas containing carbon (C) and a halogen (Ha). Or, the halogen-containing precursor gas is a gas containing carbon (C), hydrogen (H) and a halogen (Ha). In other words, the halogen-containing precursor gas is a gas represented by the chemical formula C α H β Ha γ where Ha is a halogen, α and γ are integers of 1 or more, and β is 0 or an integer of 1 or more. Here, the halogen (Ha) is one selected from Cl, F, Br, and I.

[0030] Specifically, the halogen-containing precursor gas is C 2 H 2 Cl 2 , C 2 HCl 3 , CCl4 is one selected from.

[0031] The second process gas may also contain an additive gas and / or an inert gas. The additive gas may be H 2 , C 2 H 2 , HCl. The inert gas is He, Ar, Ne, Xr, N 2 At least one gas selected from the group consisting of

[0032] An example of a recipe for the process of forming the halogen-containing layer 220 is shown below. Plasma type: CCP, 13.56MHz, 10W~500W Mounting table temperature: 250℃ or less Pressure inside processing vessel: 100mTorr~20Torr

[0033] In step S104, it is determined whether the processes of steps S102 and S103 have been repeated a predetermined number of times. If they have not been repeated the predetermined number of times (S103: NO), the process returns to step S102, and the formation of the metal-containing layer 210 (S102) and the formation of the halogen-containing layer 220 (S103) are repeated. If they have been repeated the predetermined number of times (S103: YES), the process proceeds to step S105. Here, the control unit 9 controls a transfer device (not shown) to transfer the substrate W out of the processing chamber 2 of the substrate processing apparatus 1.

[0034] Through the above processing, a resist film 230 having a layered structure (in other words, a laminate structure) in which thin metal-containing layers 210 and thin halogen-containing layers 220 are alternately stacked is formed on the underlayer 200 of the substrate W. The process of forming the metal-containing layer 210 on the substrate W (step S102) and the process of forming the halogen-containing layer 220 on the substrate W (step S103) are performed in the same processing vessel 2 (see FIG. 1).

[0035] The thickness of one metal-containing layer 210 is preferably 2 nm or less. The thickness of one halogen-containing layer 220 is preferably 2 nm or less. The thickness of the laminated resist film 230 is preferably 20 nm or less, more preferably 15 nm or less. By laminating thin films, as described later with reference to FIG. 5, the secondary electrons 312 emitted from the metal that absorbed EUV 311 can be efficiently delivered to the halogen-containing layer 220 above the metal-containing layer 210 and the halogen-containing layer 220 below the metal-containing layer 210. The halogen and hydrogen dissociated by the secondary electrons 312 can be efficiently delivered to the metal-containing layer 210 above the halogen-containing layer 220 and the metal-containing layer 210 below the halogen-containing layer 220.

[0036] 2, the substrate processing method is described as forming the metal-containing layer 210 first, then forming the halogen-containing layer 220, and repeating the above steps, but is not limited to this. The substrate processing method may be configured to form the halogen-containing layer 220 first, then forming the metal-containing layer 210, and repeating the above steps.

[0037] In the example shown in FIG. 3(a), the bottom layer of the resist film 230 (the layer in contact with the underlayer 200) is the metal-containing layer 210. That is, the metal-containing layer 210 is formed on the underlayer 200, and the halogen-containing layer 220 is formed on the metal-containing layer 210. The structure of the resist film 230 is not limited to this. The bottom layer of the resist film 230 may be the halogen-containing layer 220. That is, the halogen-containing layer 220 is formed on the underlayer 200, and the metal-containing layer 210 is formed on the halogen-containing layer 220. In addition, in FIG. 3, the top layer of the resist film 230 is the metal-containing layer 210, but the top layer of the resist film 230 may be the halogen-containing layer 220.

[0038] In step S105, an EUV exposure process is performed on the substrate W on which the resist film 230 having a laminated structure is formed on the underlayer 200. Here, in a nitrogen atmosphere, the resist film 230 of the substrate W is irradiated with EUV (Extreme Ultraviolet) through a photomask having a predetermined pattern, and an exposed portion 310 (see FIG. 3(b)) irradiated with EUV and an unexposed portion 320 (see FIG. 3(b)) not irradiated with EUV are formed in the resist film 230.

[0039] In step S106, a development process is performed on the substrate W that has been subjected to the EUV exposure process. Here, the development process selectively removes the exposed portion 310 (see FIG. 3(c)) of the resist film 230. The development process can be at least one of a wet process and a dry process.

[0040] When the development process is a wet process, the substrate W is exposed to an organic solvent to selectively remove the exposed portion 310 of the resist film 230. The organic solvent may be, for example, alcohol.

[0041] When the development process is a dry process, the substrate W is exposed to a halogen-containing gas to selectively remove the exposed portion 310 (see FIG. 3(c)) of the resist film 230. The halogen-containing gas may be at least one of HBr and HCl.

[0042] In step S107, the substrate W that has been subjected to the development process is subjected to a water vapor bake process. Here, the substrate W that has been subjected to the development process is heat-treated (baked) in a water vapor atmosphere. By performing the heat treatment in the water vapor atmosphere, the resist film 230 in the unexposed portion 320 is oxidized.

[0043] Moreover, after the heat treatment is performed in a water vapor atmosphere, a further heat treatment may be performed in a nitrogen atmosphere.

[0044] As described above, according to the substrate processing method shown in FIG.

[0045] Here, the resist film 230 formed in the substrate processing apparatus 1 can be a positive resist film capable of selectively removing the exposed portion 310. For example, when forming a contact hole or the like in the underlayer 200, a positive resist film can be preferably used as compared with a negative resist film.

[0046] Moreover, the resist film 230 formed in the substrate processing apparatus 1 can be formed by a chemical vapor deposition method using plasma. This allows the resist film to be formed thinner than a resist film formed by applying a polymer.

[0047] Furthermore, by forming the resist film 230 to be thin, when a pattern is formed on the underlayer 200 using the resist film 230 having an opening pattern as a mask, it is possible to suppress the occurrence of pattern collapse on the underlayer 200.

[0048] <Resist film processing> Next, the processing of the resist film 230 formed by the substrate processing apparatus 1 will be further described with reference to Fig. 4 to Fig. 6. Fig. 4 is a diagram showing a structure of the resist film 230 having a laminated structure formed by the substrate processing apparatus 1 according to the present embodiment. Fig. 5 is a diagram showing a structure of the resist film 230 of the exposed portion 310 in each process. Fig. 6 is a diagram showing a structure of the resist film 230 of the unexposed portion 320 in each process.

[0049] In addition, in FIGS. 4 to 6 and the following description, tetramethyltin: Sn(CH 3 ) 4 As a halogen-containing precursor gas, chloroethylene:C 2 H 2 Cl 2 An example will be described using the case where

[0050] As shown in FIG. 4, the process of step S102 3 ) 4The metal-containing layer 210 is formed by bonding the C 2 H 2 Cl 2 are bonded to form a halogen-containing layer 220. Then, by repeating the process of step S102 and the process of step S103, the metal-containing layer 210 and the halogen-containing layer 220 are alternately laminated to form a resist film 230 (see FIG. 3(a)).

[0051] Next, in step S105, an exposure process is performed on the substrate W. Here, the resist film 230 of the substrate W is irradiated with EUV having a wavelength of 13 nm and high-energy photons of 95 eV through a photomask having a predetermined pattern, thereby performing the exposure process.

[0052] 5(a) and 5(b) are diagrams showing a schematic structure of the resist film 230 of the exposed portion 310 during the exposure process. As shown in Fig. 5(a), the EUV light 311 irradiated to the substrate W is absorbed by the metal atoms (Sn) of the metal-containing layer 210, and secondary electrons 312 are emitted from the metal atoms (Sn).

[0053] The emitted secondary electrons 312 activate the Sn-C bonds between the metal atoms (Sn) and the carbon (C) around the metal atoms (Sn). The emitted secondary electrons 312 reach the upper and lower halogen-containing layers 220 from the metal-containing layer 210, activating the C-Cl bonds and C-H bonds of the halogen-containing layers 220 and releasing halogen (Cl) and hydrogen (H). The halogen-containing layer 220 is preferably a halogen-containing polymer layer containing many C-H bonds. The halogen-containing layer 220 containing many hydrogen (H) easily decomposes when exposed to EUV or secondary electrons, releasing halogen (Cl) and hydrogen (H).

[0054] The halogen (Cl) and hydrogen (H) released from the halogen-containing layer 220 are bonded to the activated metal atoms (Sn) of the metal-containing layer 210, and some of the stable Sn-C bonds are transformed into SnH N Cl M(at least one of N and M is an integer of 1 or more). This changes to an unstable structure that is released in the subsequent development process. In addition, the metal-containing layer 210 is preferably a metal-containing polymer layer containing many C-H bonds. The metal-containing polymer layer containing many C-H bonds bonds with halogen (Cl) and hydrogen (H) released from the halogen-containing layer 220, improving its solubility in the development process.

[0055] 6(a) and 6(b) are diagrams showing the structure of the resist film 230 in the unexposed portion 320 during the exposure process. As shown in Fig. 6(a) and 6(b), the metal-containing layer 210 and the halogen-containing layer 220 in the unexposed portion 320 maintain a stable and strong bond, similar to the state shown in Fig. 4.

[0056] Next, in step S106, the substrate W is subjected to a development process.

[0057] Fig. 5(c) is a diagram showing a schematic structure of the resist film 230 of the exposed portion 310 during the development process. In the exposed portion 310, as shown in Fig. 5(b), the structure is changed to an unstable structure by the exposure process, and as shown in Fig. 5(c), the resist film 230 of the exposed portion 310 is dissolved and removed.

[0058] Fig. 6(c) is a diagram showing a structure of the resist film 230 in the unexposed portion 320 during the development process. In the unexposed portion 320, as shown in Fig. 6(b), stable and strong bonds are maintained even after the exposure process, and as shown in Fig. 6(c), the resist film 230 in the unexposed portion 320 remains without being removed by the development process.

[0059] Next, in step S107, the substrate W is subjected to an oxidative annealing process (steam baking process). FIG. 6(d) is a diagram showing a schematic structure of the resist film 230 in the unexposed portion 320 in the oxidative annealing process. Here, the oxidative annealing process is performed using an oxidizing agent (O 2 and / or H 2O) is supplied to the substrate W to perform an annealing treatment. As a result, the thin metal-containing layer 210 containing the metal atom Sn is changed into an oxide film of a stable metal oxide (SnO). That is, the metal-containing layer 210 becomes a SnOCH film. The metal oxide film has excellent etching resistance even in dry etching. Therefore, the underlayer 200 can be suitably dry-etched using the resist film 230 that has been changed into a metal oxide film as a mask. In other words, the resist film 230 functions as a hard mask. As a result, the process of forming a hard mask between the resist film and the underlayer 200 to be processed can be eliminated, and the cost of substrate processing can be reduced.

[0060] In addition, the case where the resist film 230 in which the metal-containing layer 210 and the halogen-containing layer 220 are alternately laminated is formed by the plasma CVD method has been described as an example, but the present invention is not limited thereto. A configuration in which the resist film 230 in which the metal-containing layer 210 and the halogen-containing layer 220 are alternately laminated by the thermal CVD method may be used. Also, a process in which the resist film 230 in which the metal-containing layer 210 and the halogen-containing layer 220 are alternately laminated by using remote plasma may be used. Also, the metal-containing layer 210 and the halogen-containing layer 220 may be formed by different film formation methods. Also, the metal-containing layer 210 may be formed by physical vapor deposition (PVD).

[0061] The metal-containing precursor gas may be a gas containing a halogen (Ha) in addition to a metal (M), carbon (C), and hydrogen (H). W Ha X C Y H Z where M is a metal, Ha is a halogen, W is an integer of 1 or more, and X, Y, and Z are 0 or integers of 1 or more. Specifically, the metal-containing precursor gas is SnH 4 , SnH 3 Cl, SnCl 3 C 4 H 9 , AlCl 3 , Al(C 2 H5 ) 2 Cl, TiCl 4 , TaCl 5 , GeH 4 , Ge(CH 3 ) 4 is one selected from.

[0062] The metal-containing precursor gas may be a gas containing nitrogen (N) and / or oxygen (O) in addition to metal (M), carbon (C), and hydrogen (H). V N W H X C Y O Z where M is a metal, V is an integer of 1 or more, and W, X, Y, and Z are 0 or integers of 1 or more. Specifically, the metal-containing precursor gas is Sn(N(CH 3 ) 2 ) 4 , Sn(OC 4 H 9 ) 4 , Al(N(CH 3 ) 2 ) 3 , Ti(N(CH 3 ) 2 ) 4 , Ta(N(CH 3 ) 2 ) 5 , Hf(N(CH 3 ) 2 ) 4 , Al(CH 3 ) 2 O.C. 3 H 7 is one selected from.

[0063] The metal-containing precursor gas may also be a combination of these gases.

[0064] The second process gas is represented by the chemical formula C α H β Ha γ and a halogen-containing precursor gas represented by the chemical formula C X H YIn addition, Ha is a halogen, α and γ are integers of 1 or more, and β is 0 or an integer of 1 or more. Here, the halogen (Ha) is one selected from Cl, F, Br, and I. In addition, X and Y are integers of 1 or more. For example, the additive gas is C 2 H 2 and the second process gas is C 2 H 2 Cl 2 and C. 2 H 2 By adding an additive gas to the second process gas, a stable halogen-containing layer can be formed.

[0065] The second process gas is represented by the chemical formula C α H β Ha γ and a halogen-containing precursor gas represented by the chemical formula C X H Y and the chemical formula Ha M H N In addition, Ha is a halogen, α and γ are integers of 1 or more, and β is an integer of 0 or 1 or more. Here, the halogen (Ha) is one selected from Cl, F, Br, and I. In addition, X and Y are integers of 1 or more. In addition, M is an integer of 1 or more, and N is an integer of 0 or 1 or more. For example, the additive gas is C 2 H 2 And, Cl 2 HCl. The second process gas is a mixture of C 2 H 2 Cl 2 , C 2 H 2 , and Cl 2 Mixture of gases, C 2 H 2 Cl 2 , C 2 H 2 The additive gas may be a mixture of H2O, HCl, and the second process gas, and a stable halogen-containing layer can be formed by adding an additive gas to the second process gas.

[0066] The resist film 230 may have a structure in which the metal-containing layer 210, the halogen-containing layer 220, and an organic film (hydrocarbon layer) are laminated. That is, the process of forming a laminated structure film (resist film) may further include a process of forming a hydrocarbon layer (not shown) on the substrate W in addition to a process of forming a metal-containing layer 210 on the substrate W (see step S102) and a process of forming a halogen-containing layer 220 on the substrate W (see step S103), and these processes may be repeated to form a laminated structure film (resist film) on the substrate W. The process of forming a hydrocarbon layer (not shown) on the substrate W is preferably performed after the process of forming the metal-containing layer 210 on the substrate W (see step S102) and before the process of forming the halogen-containing layer 220 on the substrate W (see step S103). By forming a hydrocarbon layer between the metal-containing layer 210 and the halogen-containing layer 220, the reaction between the metal of the metal-containing layer 210 and the halogen of the halogen-containing layer 220 can be suppressed. The uppermost layer of the resist film 230 may be the halogen-containing layer 220 or a thick layer of an organic film (hydrocarbon layer), which can prevent natural oxidation of the metal-containing layer 210 before the exposure and development processes.

[0067] The above describes the substrate processing apparatus 1 and the substrate processing method according to this embodiment, but the present disclosure is not limited to the above-described embodiments, and various modifications and improvements are possible within the scope of the gist of the present disclosure described in the claims. [Explanation of symbols]

[0068] 1. Substrate Processing Equipment 200 Base layer 210 Metal-containing layer 220 Halogen-containing layer 230 Resist film (laminated structure film) 310 Exposure Section 311 EUV 312 Secondary electron 320 Unexposed area W substrate

Claims

1. forming a laminated structure film on a substrate, the laminated structure film including a metal-containing layer and a halogen-containing layer; a step of irradiating the laminated structure film with extreme ultraviolet rays in a predetermined pattern to form an exposed portion irradiated with the extreme ultraviolet rays and an unexposed portion not irradiated with the extreme ultraviolet rays in the laminated structure film; and selectively removing the exposed portion of the laminated structure film. A method for processing a substrate.

2. The metal-containing layer is providing a first process gas comprising a metal-containing precursor gas to generate a plasma; and exposing the substrate to the generated plasma to form the metal-containing layer; The method for processing a substrate according to claim 1 .

3. The metal-containing precursor gas is Chemical formula M Ｘ C Ｙ H Ｚ It is expressed as M is a metal, X and Z are integers of 1 or more, and Y is 0 or an integer of 1 or more; The substrate processing method according to claim 2 .

4. The metal-containing precursor gas is Chemical formula M Ｗ Ha Ｘ C Ｙ H Ｚ It is expressed as M is a metal, Ha is a halogen, W is an integer of 1 or more, and X, Y, and Z are each 0 or an integer of 1 or more. The substrate processing method according to claim 2 .

5. The metal-containing precursor gas is Chemical formula M Ｖ N Ｗ H Ｘ C Ｙ O Ｚ It is expressed as M is a metal, V is an integer of 1 or more, and W, X, Y, and Z are each 0 or an integer of 1 or more; The substrate processing method according to claim 2 .

6. The metal (M) is one selected from Sn, Sb, In, Al, Ti, Mn, Ta, Hf, and W; The substrate processing method according to any one of claims 3 to 5.

7. The metal-containing precursor gas is Sn(CH ３ ), SnH(CH ４ ), SnH ３ )(CH ３ ), Sn(C ２ H ３ )(CH ２ ), Al(CH ２ ), Co(C ５ H ４ ), SnR ３ ), SnHR ３ ), (wherein, R is -CH ５ ), -C ５ H ２ ), -C ４ H ３ ), -C ３ H ２ ), -C ３ H ３ ), -C ５ H ４ ), -C ７ H ６ ), -C ６ H ４ ), SnH ３ ), SnH ３ Cl, SnCl ４ C ９ H ３ ), AlCl ２ ), Al(C ５ H ２ Cl, TiCl ４ ), TaCl ５ ), GeH ４ ), Ge(CH ３ )(CH ４ ), Sn(N(CH ３ )(CH ２ )(CH ４ ), Sn(O-C ４ H ９ )(CH ４ ), Al(N(CH ３ )(CH ２ )(CH ３ ), Ti(N(CH ３ )(CH ２ )(CH ４ ), Ta(N(CH ３ )(CH ２ )(CH ５ ), Hf(N(CH ３ )(CH ２ )(CH ４ ), Al(CH ３ )(CH ２ OC ３ H ７ One selected from The substrate processing method according to claim 2 .

8. The halogen-containing layer is providing a second process gas comprising a halogen-containing precursor gas to generate a plasma, and exposing the substrate to the generated plasma to form the halogen-containing layer; The method for processing a substrate according to claim 1 .

9. The halogen-containing precursor gas is Chemical formula C α H β Ha γ It is expressed as Ha is a halogen, α and γ are integers of 1 or more, and β is 0 or an integer of 1 or more; The substrate processing method according to claim 8 .

10. The halogen (Ha) is one selected from Cl, F, Br, and I; The substrate processing method according to claim 9 .

11. The halogen-containing precursor gas is C ２ H ２ C ２ , C ２ HCl ３ , CCl ４ One selected from The substrate processing method according to claim 8 .

12. The second process gas further includes an additive gas. The substrate processing method according to claim 8 .

13. The additive gas is represented by the chemical formula C Ｘ H Ｙ It is expressed as X and Y are integers of 1 or more; The method of claim 12.

14. The additive gas is represented by the chemical formula C Ｘ H Ｙ and the chemical formula Ha Ｍ H Ｎ It is expressed as Ha is a halogen; X, Y, and M are integers of 1 or more; N is 0 or an integer of 1 or more; The halogen (Ha) is one selected from Cl, F, Br, and I; The method of claim 12.

15. The additive gas is C ２ H ２ That is, The method of claim 12.

16. The additive gas is C ２ H ２ and Cl ２ or a mixture of C ２ H ２ and HCl, The method of claim 12.

17. The step of forming the laminated structure film includes: forming the metal-containing layer on the substrate; and forming the halogen-containing layer on the metal-containing layer. The method of claim 1 .

18. The step of forming the laminated structure film includes: forming the halogen-containing layer on the substrate; and forming the metal-containing layer on the halogen-containing layer. The method of claim 1 .

19. The step of forming the laminated structure film includes: The step of forming the metal-containing layer and the step of forming the halogen-containing layer are repeated a plurality of times. The method of claim 1 .

20. The step of forming the metal-containing layer and the step of forming the halogen-containing layer are performed in the same processing vessel. The method of claim 19.

21. The step of forming the laminated structure film includes: forming a hydrocarbon layer; The method of claim 1 .

22. The step of forming the hydrocarbon layer comprises: is carried out after the step of forming the metal-containing layer and before the step of forming the halogen-containing layer; The method of claim 21 .

23. The step of forming the laminated structure film includes: forming the halogen-containing layer or the hydrocarbon layer on the top layer; The method of claim 21 .

24. The step of forming the metal-containing layer and the step of forming the halogen-containing layer include Processed at a temperature of 250° C. or less; The method of claim 1 .

25. The thickness of one of the metal-containing layers is 2 nm or less, The thickness of one of the halogen-containing layers is 2 nm or less. The method of claim 1 .

26. The thickness of the laminated structure film is 15 nm or less. The method of claim 1 .

27. The step of irradiating the laminated structure film with extreme ultraviolet light includes: Processed under nitrogen atmosphere, The method of claim 1 .

28. The step of selectively removing the exposed portion includes: A wet process in which the substrate is exposed to an organic solvent to selectively remove the exposed portion. The method of claim 1 .

29. The step of selectively removing the exposed portion includes: a dry process in which the substrate is exposed to a halogen-containing gas to selectively remove the exposed areas; The method of claim 1 .

30. The method further comprises a step of heat treating the substrate after selectively removing the exposed portion. The method of claim 1 .

31. The step of heat treating the substrate includes: Heat treatment in a water vapor atmosphere. The method of claim 1 .

32. The method further comprises a step of heat-treating the substrate in a nitrogen atmosphere after the heat treatment in the water vapor atmosphere. The method of claim 31 .

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