Substrate processing method and substrate processing apparatus

Abstract

The present invention provides a substrate processing method including a step of developing a substrate on which a negative metal-containing resist coating film has been formed, and which has been subjected to an exposure treatment and a heat treatment after the exposure treatment, using a polar developing material and a non-polar developing material.

Description

Technical Field

[0001] The invention relates to a substrate processing method and a substrate processing device. Background Art

[0002] Patent Document 1 discloses a method of forming a developed patterned layer including an organic metal oxide / hydroxide network by developing an organic metal patterned layer exposed to radiation.

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application No. 2022-526031 Summary of the invention

[0006] Technical problem to be solved by the invention

[0007] The technology of the present invention aims to improve the exposure sensitivity of a metal resist-containing coating. In addition, the technology of the present invention also aims to reduce the residue remaining on a substrate when a metal resist-containing pattern is formed.

[0008] Technical solutions for solving technical problems

[0009] A substrate processing method according to an embodiment of the present invention includes a step of developing a substrate on which a negative metal-containing resist film is formed and subjected to an exposure treatment and a heat treatment after the exposure treatment, using a polar developing material and a non-polar developing material.

[0010] Effects of the Invention

[0011] According to the present invention, the exposure sensitivity of a coating film containing a metal resist can be improved. In addition, according to the present invention, the residue remaining on a substrate during pattern formation of a metal resist can be reduced. BRIEF DESCRIPTION OF THE DRAWINGS

[0012] Figure 1 This is a schematic explanatory diagram showing the internal structure of a wafer processing apparatus as a substrate processing apparatus according to the present embodiment.

[0013] Figure 2 This is a diagram schematically showing the internal structure of the front side of the wet processing section.

[0014] Figure 3 It is a diagram schematically showing the internal structure of the back side of the wet processing section.

[0015] Figure 4 It is a rough representation Figure 1 A cross-sectional view of an interface block portion of a wafer processing device.

[0016] Figure 5 This is a flowchart showing the main steps of Example 1 of the processing procedure.

[0017] Figure 6 It is a diagram for explaining the intermediate exposure region and is a partially enlarged cross-sectional view schematically showing the metal-containing resist film after exposure.

[0018] Figure 7 This is a graph comparing the thickness of the metal-containing resist film after development in the case of developing with a non-polar developing material and then developing with a polar developing material as in Example 1 of the processing order and in the case of developing with only a non-polar developing material.

[0019] Figure 8 This is a flowchart showing main steps of Modification 1 of Example 1 of the processing procedure.

[0020] Fig. 9 This is a graph comparing the thickness of the metal-containing resist film after development when development is performed like Modification 1 of Example 1 of the process order and when only non-polar development is performed.

[0021] Fig.10 This is a diagram showing the relationship between the CD of a metal-containing resist pattern after development and the exposure amount.

[0022] Fig.11 This is a diagram showing the relationship between the CD of a pattern containing a metal resist after development and the roughness of the pattern.

[0023] Fig.12 This is a diagram showing the relationship between the CD of a metal-containing resist pattern after development and the ratio of defects.

[0024] Fig.13 This is a diagram showing an example of the structure of a developing module that performs both non-polar development and polar development.

[0025] Fig.14 This is a flowchart showing the main steps of Example 2 of the processing sequence.

[0026] Fig.15 This is a flowchart showing main steps of Modification Example 1 of Example 2 of the processing order.

[0027] Fig.16 This is a flowchart of main steps of Modification Example 2 of Example 2 showing the processing order.

[0028] Fig.17 This is a flowchart showing the main steps of Example 3 of the processing sequence.

[0029] Fig.18 : is a figure for explaining the reason why Example 3 using the processing order can suppress pattern collapse.

[0030] Fig.19 This is a flowchart showing the main steps of Example 4 of the processing sequence.

[0031] Fig. 20 This is a flowchart showing the main steps of Example 5 of the processing sequence.

[0032] Fig.21 This is a graph comparing the thickness of the metal-containing resist film after development when ultraviolet irradiation and development using a polar developing material are performed as in Example 5 of the processing order, and when development using only a non-polar developing material is performed without ultraviolet irradiation.

[0033] Fig. 22 This is a diagram showing the relationship between the CD of a metal-containing resist pattern after development and the exposure amount.

[0034] Fig.23 This is a diagram showing the relationship between the CD of a pattern containing a metal resist after development and the roughness of the pattern.

[0035] Fig.24 This is a diagram showing the relationship between the CD of a metal-containing resist pattern after development and the ratio of defects.

[0036] Fig.25 This is a graph showing the relationship between CD and exposure amount when a columnar metal-containing resist pattern with a target width of 18 nm is formed.

[0037] Fig.26 This is a diagram showing the relationship between the CD of a pattern containing a metal resist after development and the roughness of the pattern.

[0038] Fig. 27 This is a diagram showing the relationship between the CD of a metal-containing resist pattern after development and the ratio of defects.

[0039] Fig.28 This is a flowchart of main steps of Modification Example 1 of Example 5 showing the processing order.

[0040] Fig.29 This is a flowchart of the main steps of the second variant of the fifth example showing the processing order.

[0041] Fig.30 This is a flowchart of the main steps of Modification Example 3 of Example 5 showing the processing order. DETAILED DESCRIPTION

[0042] In the manufacturing process of semiconductor devices, a series of processes are performed to form a resist pattern on a substrate such as a semiconductor wafer (hereinafter referred to as a "wafer"). The series of processes includes, for example, a resist coating process of supplying a resist onto the substrate to form a resist coating (hereinafter referred to as a resist film), an exposure process of exposing the resist film to a predetermined pattern, a PEB (PostExposure Bake) process of heating the resist film after exposure for the purpose of promoting a chemical reaction in the resist film after exposure, and a development process of developing the resist film after exposure to form a resist pattern.

[0043] As a resist, chemically amplified resists have been widely used, but in recent years, negative metal-containing resists are sometimes used. However, when a metal-containing resist is used to form a resist pattern, sometimes residues remain on the substrate due to the developer (e.g., organic solvent) used in the development process. In addition, if a developer with a high residue removal ability is used, although it is not easy to leave residues on the substrate, it may cause the coating of the metal-containing resist (hereinafter referred to as the metal-containing resist film) to be overdeveloped, that is, the exposure sensitivity of the metal-containing resist film is reduced. When the temperature during PEB treatment is increased in order to increase the exposure sensitivity of the metal-containing resist film, the amount of residue remaining on the substrate may increase.

[0044] Therefore, the technology of the present invention aims to achieve both an increase in the exposure sensitivity of a metal-containing resist film and a decrease in the amount of residue remaining on a substrate when the metal-containing resist is patterned.

[0045] Hereinafter, a substrate processing method and a substrate processing apparatus according to the present embodiment will be described with reference to the accompanying drawings. In this specification and the accompanying drawings, elements having substantially the same functional structure are given the same reference numerals to avoid repeated description.

[0046] <Wafer processing equipment>

[0047] Figure 1 This is an explanatory diagram schematically showing the internal structure of a wafer processing apparatus as a substrate processing apparatus according to the present embodiment. Figure 2 and Figure 3 These are diagrams schematically showing the internal structures of the front side and the back side of a wet processing section described later. Figure 4 It is a rough representation Figure 1 A cross-sectional view of a handover block portion described later in a wafer processing device.

[0048] Figure 1The wafer processing device 1 is used to form a negative metal-containing resist pattern on a wafer W as a substrate, specifically, to form a negative metal-containing resist pattern with a pitch of 50 nm or less. The metal contained in the negative metal-containing resist may be any metal, but in this embodiment, it is a metal constituting a complex, more specifically, for example, tin, hafnium, tellurium, bismuth, indium, antimony, iodine, germanium or a combination thereof.

[0049] The wafer processing apparatus 1 includes, for example, a wet (liquid phase) processing section 2 , a dry (gas phase) processing section 3 , and a transfer and transport section 4 .

[0050] Wet treatment section 2 Figures 1 to 3 As shown, the wet processing section 2 includes a box station 10, a processing station 11 and an interface station 12, which are connected to an exposure device E. The exposure device E performs exposure processing on the wafer W, specifically, for example, using EUV (Extreme Ultra-Violet) light for exposure processing. In the wet processing section 2, the box station 10, the processing station 11 and the interface station 12 are connected as a whole.

[0051] In addition, hereinafter, the connection direction between the wet processing section 2 and the exposure device E is referred to as a width direction, and a direction perpendicular to the connection direction, that is, the width direction, as seen from a plan view is referred to as a depth direction.

[0052] The cassette station 10 of the wet processing unit 2 is a portion for carrying in and out a cassette C, which is a storage container configured to be able to store a plurality of wafers W.

[0053] The box station 10 is provided on one side in the width direction, for example ( Figure 1 A box mounting table 20 is provided at the end of the box mounting table 20 (negative side in the Y direction, etc.). A plurality of, for example, four, mounting plates 21 are provided on the box mounting table 20. The mounting plates 21 are arranged in the depth direction ( Figure 1 These mounting plates 21 can mount the boxes C when the boxes C are carried in and out of the wet processing unit 2.

[0054] In addition, the cassette station 10 is provided on the other side in the width direction ( Figure 1 A conveying module 23 for conveying wafer W is provided on the positive side of the Y direction. The conveying module 23 has a structure that is configured to Figure 1 The conveying module 23 includes a conveying arm 23a that is movable in the vertical direction and in the direction around the vertical axis. The conveying module 23 can convey the wafer W between the box C on each loading plate 21 and the delivery module 51 of the delivery tower 50 described later.

[0055] In addition, the cassette station 10 may be located above the cassette stage 20 and at a portion ( Figure 1A storage portion (not shown) for placing and storing the boxes C is provided on the negative side portion in the Y direction.

[0056] The processing station 11 includes a plurality of various processing modules for performing predetermined processing such as development processing.

[0057] The processing station 11 is divided into a plurality of (two in the example shown in the figure) blocks, each of which includes various modules. A processing block BL1 is provided on the interface station 12 side, and a delivery block BL2 is provided on the cassette station 10 side.

[0058] The processing block BL1 is, for example, on the front side ( Figure 1 The first block G1 is provided on the negative side of the X direction, and the depth side ( Figure 1 A second block G2 is provided on the positive side in the X direction.

[0059] For example, in the first block G1, Figure 2 As shown, a plurality of liquid processing modules are sequentially arranged from the bottom, such as a first developing module 30, a second developing module 31, a third developing module 32 and a resist coating module 33. The first to third developing modules 30 to 32 are all wet developing units for wet developing the wafer W. The resist coating module 33 is a resist coating unit for coating a negative metal-containing resist on the wafer W to form a metal-containing resist film.

[0060] The first developing module 30 develops the wafer W using a non-polar developing material.

[0061] The non-polar developing material is, for example, an organic solvent composed of molecules having an ester structure or an ether structure, or a mixture of the above organic solvent and an acidic material.

[0062] The organic solvent is, for example, methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, methoxyethyl acetate, ethoxyethyl acetate, 2-heptanone, propylene glycol monomethyl ether acetate (PGMEA), isopropanol, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol Monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-prop Oxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, carbonate Ethyl ester, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, propyl-3-methoxypropionate, or a combination of two or more thereof.

[0063] In addition, the acidic material is an organic acid, an inorganic acid or a combination thereof. The organic acid is, for example, an organic carboxylic acid such as acetic acid and citric acid.

[0064] As the non-polar developing material, butyl acetate, 2-heptanone, PEGMEA, or a mixture of any of these materials and an organic acid can be preferably used.

[0065] The second developing module 31 develops the wafer W using a polar developing material.

[0066] The polar developing material is, for example, a solution of an alkaline material.

[0067] The above-mentioned alkaline materials are, for example, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia water, first amines such as ethylamine and n-propylamine, second amines such as diethylamine and di-n-butylamine, third amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, tetrapropylammonium hydroxide, methyltriethylammonium hydroxide, trimethylethylammonium hydroxide, dimethyldiethylammonium hydroxide, trimethyl(2-hydroxyethyl)ammonium hydroxide (i.e., choline), triethyl(2-hydroxyethyl)ammonium hydroxide, dimethyldi(2-hydroxyethyl)ammonium hydroxide, diethyldi(2-hydroxyethyl)ammonium hydroxide, methyltri(2-hydroxyethyl)ammonium hydroxide, ethyltri(2-hydroxyethyl)ammonium hydroxide, tetra(2-hydroxyethyl)ammonium hydroxide and other quaternary ammonium salts, and cyclic amines such as pyrrole and piperidine.

[0068] The solvent of the solution of the alkaline material is water, for example, and in this case, an alcohol such as isopropyl alcohol or a surfactant such as a nonionic surfactant may be added in an appropriate amount.

[0069] Alternatively, alcohols (eg, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, ethane-1,2-diol, propane-1,2,3-triol, etc.) may be used as solvents for the solution of the alkaline material.

[0070] The polar developing material may also be water. Specifically, the polar developing material may be neutral water or deionized water.

[0071] In addition, the polar developing material can also be a mixture of water and an acidic material, wherein the acidic material is an organic sulfonic acid, an organic carboxylic acid (such as acetic acid, citric acid, etc.), an inorganic acid or a combination thereof.

[0072] As the polar developing material, a quaternary ammonium salt solution is preferably used, and a tetraethylammonium hydroxide solution or a tetrabutylammonium hydroxide solution is more preferably used. The concentration of the tetraethylammonium hydroxide solution or the tetrabutylammonium hydroxide solution is preferably 0.1% to 70% (parts by weight), and more preferably 2% to 10% (parts by weight).

[0073] In addition, neutral water or deionized water is preferably used as the polar developing material because of low material cost, small environmental load, and the ability to omit rinsing treatment after development.

[0074] The third developing module 32 develops the wafer W using a mixture of a non-polar developing material and a polar material.

[0075] For example, four first to third developing modules 30 to 32 and four resist coating modules 33 are arranged in the width direction (Y direction in the figure). The number and arrangement of the first to third developing modules 30 to 32 and four resist coating modules 33 can be arbitrarily selected.

[0076] The first to third developing modules 30 to 32 and the resist coating module 33 apply a predetermined processing liquid onto the wafer W by, for example, spin coating. In spin coating, the processing liquid is discharged onto the wafer W from, for example, a discharge nozzle, and the wafer W is rotated to spread the processing liquid on the surface of the wafer W.

[0077] In addition, the first to third developing modules 30 to 32 may have a rinsing nozzle. For example, when a tetraethylammonium hydroxide solution or a tetrabutylammonium hydroxide solution is used as a developing material (specifically, a developing solution), after a liquid film of the developing solution is formed on the wafer W by spin coating, deionized water is spitted onto the wafer W as a rinsing solution to remove the developing solution from the wafer W, and then the wafer W is rotated to dry it. In addition, when neutral water or deionized water is used as a developing solution, after a liquid film of the developing solution is formed on the wafer W by spin coating, the wafer W may be rotated to dry it without the rinsing process.

[0078] For example, in the second block G2 Figure 3 As shown, a plurality of heat treatment modules 40 and ultraviolet irradiation modules 45 are arranged in the vertical direction (up and down direction in the figure) and the width direction (Y direction in the figure). The number and arrangement of the heat treatment modules 40 and ultraviolet irradiation modules 45 can also be arbitrarily selected.

[0079] For example, at least a portion of the heat treatment module 40 is a module that is connected to a heating portion for heating the wafer W and a cooling portion for cooling the wafer W. In the heat treatment module 40, the heating portion is Figure 1 The heat plate 41 is shown, and the cooling part has a cooling plate 42. The heat plate 41 is configured to be able to carry a wafer W, and a heating mechanism such as a resistance heating heater is provided inside the heat plate 41, and the cooling plate 42 is configured to be able to carry a wafer W, and a cooling mechanism such as a flow path for a cooling refrigerant is provided inside the heat plate 41.

[0080] Furthermore, the ultraviolet irradiation module 45 is used to irradiate ultraviolet rays onto the wafer W. Specifically, ultraviolet rays are irradiated onto the entire upper surface of the wafer W in a moisture-containing atmosphere, that is, onto at least the entire device formation region of the wafer W.

[0081] Processing block BL1 is as follows Figure 1 As shown, a conveying path R1 extending in the width direction is provided between the first block G1 and the second block G2. In the processing block BL1, a plurality of first to third developing modules 30 to 32 and a resist coating module 33 are arranged in a manner arranged along the conveying path R1 extending in the width direction. A conveying module R2 for conveying a wafer W is arranged in the conveying path R1.

[0082] The conveying module R2 has, for example, Figure 1The transport module R2 can transport the wafer W to the surrounding first block G1, second block G2, transfer tower 50 and transfer tower 60 by moving the transport arm R2a holding the wafer W in the wafer transport area D. The transport module R2 can transport the wafer W to the surrounding first block G1, second block G2, transfer tower 50 and transfer tower 60 described later. Figure 3 As shown, a plurality of modules are arranged vertically and horizontally, and for example, wafers W can be transported to the first block G1 , the second block G2 , and the delivery towers 50 and 60 , respectively, at the same height.

[0083] Furthermore, a shuttle transport module R3 for linearly transporting the wafer W between the delivery tower 50 and the delivery tower 60 is provided in the transport path R1 .

[0084] The shuttle module R3 can transfer the wafer W between the devices of the delivery tower 50 and the devices of the delivery tower 60 at the same height by linearly moving the supported wafer W in the Y direction.

[0085] The handover block BL2 is as follows Figure 1 As shown in FIG. 1 , a delivery tower 50 is provided in the center in the depth direction (the X direction in the figure). Specifically, the delivery tower 50 is provided in the delivery block BL2 at a position adjacent to the conveying path R1 of the processing block BL1 in the width direction (the Y direction in the figure). Figure 3 As shown, a plurality of delivery modules 51 are provided so as to overlap in the vertical direction.

[0086] Interface station 12 Figure 1 As shown, it is disposed between the processing station 11 and the exposure device E and is used for transferring the wafer W between these devices.

[0087] A transfer tower 60 is provided at a position adjacent to the conveying path R1 of the processing block BL1 in the width direction (the Y direction in the figure) in the interface station 12. Figure 3 As shown, a plurality of delivery modules 61 are provided so as to overlap in the vertical direction.

[0088] In addition, if Figure 1 As shown, a conveying module R4 is provided at the interface station 12 .

[0089] The conveying module R4 is disposed at a position adjacent to the delivery tower 60 in the width direction (the Y direction in the figure), for example, Figure 1 The transport module R4 can hold the wafer W on the transport arm R4a and transport the wafer W between the plurality of delivery modules 61 of the delivery tower 60 and the exposure device E.

[0090] Furthermore, the handover block BL2 of the processing station 11 is as follows Figure 1 As shown, a transfer tower 52 is provided at the end on the inner side (positive side in the X direction in the figure).

[0091] Transfer tower 52 Figure 4 The handover module 53 is shown. In the handover tower 52, the handover module 53 can be in the vertical direction ( Figure 4 Multiple overlaps in the up and down directions).

[0092] In addition, the transfer tower 52 may further include a cooling module 54 for cooling the wafers.

[0093] Furthermore, if Figure 1 As shown, a conveying module R5 is provided in the delivery block BL2. The conveying module R5 is provided between the delivery tower 50 and the delivery tower 52, and for example has a conveying arm R5a movable in the vertical direction and in the direction around the vertical axis. The conveying module R5 can hold the wafer W on the conveying arm R5a to convey the wafer W between the plurality of delivery modules 51 of the delivery tower 50, the plurality of delivery modules 53 of the delivery tower 52, and the cooling module 54.

[0094] The dry processing section 3 is, for example, Figure 1 As shown, there are a load lock station 100 and a processing station 101. In the dry processing unit 3, the load lock station 100 is integrally connected to the processing station 101. In this example, the connection direction of the load lock station 100 and the processing station 101 and the connection direction of the wet processing unit 2 and the exposure device E are perpendicular in the top view.

[0095] The load lock station 100 is provided with a load lock module 110 whose internal atmosphere can be switched between a reduced pressure atmosphere and an atmospheric pressure atmosphere.

[0096] The processing station 101 includes, for example, a vacuum transfer chamber 120 , first to third dry developing modules 121 to 123 , and a thermal processing module 124 .

[0097] The vacuum transfer chamber 120 is composed of a sealable (airtight) box, and its interior can be kept in a reduced pressure state (vacuum state). The vacuum transfer chamber 120 is formed, for example, in a substantially polygonal shape (a pentagonal shape in the figure) in a plan view.

[0098] The first to third dry developing modules 121 to 123 are dry developing units for dry developing the wafer W. Unlike wet processing using liquid, dry processing uses gas, specifically, uses gas under reduced pressure.

[0099] The first dry developing module 121 uses a non-polar developing material to perform dry developing on the wafer W. The non-polar developing material used by the first dry developing module 121 is, for example, the vaporized material exemplified as the non-polar developing material used by the first developing module 30 .

[0100] The second dry developing module 122 uses a polar developing material to dry develop the wafer W. The polar developing material used by the second dry developing module 122 is, for example, the vaporized substance exemplified as the polar developing material used by the second developing module 31, hydrogen bromide, boron trichloride, acetic acid (vaporized substance), or a combination of two or more thereof.

[0101] The third dry developing module 123 performs dry developing on the wafer W using a mixture of a non-polar developing material and a polar material.

[0102] The heat treatment module 124 heats the wafer W, that is, performs a heat treatment on the wafer W.

[0103] For example, one each of the first to third dry developing modules 121 to 123 and the heat treatment module 124 is provided.

[0104] In the processing station 101, the first to third dry developing modules 121~123, the heat treatment module 124 and the loading lock station 100 are arranged, for example, in a manner surrounding the vacuum transfer chamber 120 in a top view, that is, in a manner arranged around a vertical axis (axis) passing through the center of the vacuum transfer chamber 120.

[0105] In addition, a conveying module 125 for conveying a wafer W is provided inside the vacuum conveying chamber 120. The conveying module 125 includes, for example, a conveying arm 125a movable in a direction around a vertical axis. The conveying module 125 holds the wafer W on the conveying arm 125a, and can convey the wafer W between the first to third dry developing modules 121 to 123 and the load lock module 110, etc.

[0106] The transfer unit 4 transfers the wafers W between the wet processing unit 2 and the dry processing unit 3 . Specifically, the transfer unit 4 transfers the wafers W in units of wafers, that is, individually.

[0107] The transfer unit 4 is provided with a transfer path 130, through which the wafer W is transferred between the wet processing unit 2 and the dry processing unit 3. The transfer path 130 of the transfer unit 4 is a transfer path extending in the depth direction (X direction in the figure) including the delivery tower 50 of the delivery block BL2.

[0108] In this embodiment, the transfer unit 4 is connected to a portion of the wet processing unit 2 that is farther from the exposure device E than the processing block BL1, specifically, to the delivery block BL2. More specifically, the conveying path 130 of the transfer unit 4 is connected to the delivery block BL2.

[0109] A conveyance module 131 for conveying the wafer W is provided in the conveyance path 130 .

[0110] The transfer module 131 includes a transfer arm 131 a movable in the vertical direction and in the direction around the vertical axis. The transfer module 131 holds the wafer W on the transfer arm 131 a and can transfer the wafer W between the plurality of transfer modules 53 of the transfer tower 52 , the cooling module 54 , and the load lock module 110 .

[0111] Furthermore, the wafer processing device 1 has a control unit 5 for executing control of the wafer processing device 1 including control of the conveying module. The control unit 5 is, for example, a computer having a processor such as a CPU and a memory, and has a program storage unit (not shown). The program stored in the program storage unit includes instructions for the processing sequence described later. In addition, the above program can be recorded in a non-temporary storage medium H that can be read by a computer, and installed from the storage medium H to the control unit 5. The storage medium H can be temporary or non-temporary.

[0112] <Processing order example 1>

[0113] Next, an example of a processing procedure executed by the wafer processing apparatus 1 will be described. Figure 5 This is a flowchart showing the main steps of Example 1 of the processing procedure. Figure 6 It is a diagram for explaining the intermediate exposure region described later, and is a partially enlarged cross-sectional diagram schematically showing the metal-containing resist film after exposure. In addition, the following steps are executed under the control of the control unit 5 based on the program stored in the program storage unit (not shown).

[0114] First, a wafer W is introduced into the wafer processing apparatus 1 (step S1).

[0115] Specifically, for example, first, the wafer W is taken out from the cassette C placed on the cassette stage 20 by the transfer module 23 of the wet processing unit 2 and is transferred to the delivery module 51 of the delivery tower 50 of the delivery block BL2.

[0116] Next, a resist coating process is performed on the wafer W to form a metal-containing resist film on the wafer W (step S2).

[0117] Specifically, for example, the wafer W is transported by the transport module R2 to the resist coating module 33 of the processing block BL1, and a negative metal-containing resist is spin-coated on the surface of the wafer W to form a metal-containing resist film in a manner covering the surface of the wafer W. The thickness of the formed metal-containing resist film is, for example, 3 nm to 50 nm, preferably 15 nm to 30 nm.

[0118] Next, a pre-exposure baking (PAB: Pre-Applied Bake) process is performed on the wafer W (step S3).

[0119] Specifically, the wafer W is transported to the heat treatment module 40 for PAB treatment, and heat treatment is performed on the wafer W. Thereafter, the wafer W is transported to the delivery module 61 of the delivery tower 60 of the interface station 12 .

[0120] Next, the wafer W is subjected to exposure processing (step S4).

[0121] Specifically, for example, the wafer W is transported to the exposure device E by the transport module R4 , and a predetermined pattern formed on the mask is transferred to the metal-containing resist film on the wafer W by EUV light. Thereafter, the wafer W is transported to the delivery module 61 of the delivery tower 60 by the transport module R4 .

[0122] Next, the wafer W is subjected to a post-first exposure heating process (PEB process) (step S5).

[0123] Specifically, for example, the wafer W is transported by the transport module R2 to the heat treatment module 40 for the first PEB treatment, and the wafer W is subjected to a heat treatment using the hot plate 41 .

[0124] The negative metal-containing resist is in a water-repellent (waterproof) state before exposure. On the other hand, after exposure, the organic ligand of the metal complex (complex of metals such as tin, hafnium, tellurium, bismuth, indium, antimony, iodine, germanium, etc.) of the negative metal-containing resist will be detached and become active. The metal-containing resist in this active state reacts with moisture in the surrounding atmosphere, etc., and the hydroxyl group is combined with the part where the ligand is detached, thereby becoming a hydrophilic precursor. The precursorized metal-containing resist condenses and condenses, and thus the metal-containing resist becomes insoluble in the developing material.

[0125] The temperature of the wafer W during the first PEB treatment in step S5 is preferably 80° C. to 300° C., more preferably 130° C. to 250° C. The lower the temperature of the wafer W during the first PEB treatment, the smaller the roughness of the pattern surface of the metal-containing resist obtained by Example 1 of the treatment sequence (i.e., the better the uniformity of the size of the microscopic region).

[0126] The temperature of the wafer W during the first PEB treatment may be high enough to cause the above-mentioned condensation to occur, or low enough to prevent (or make it difficult for) the above-mentioned condensation to occur. Even at a low temperature to prevent condensation from occurring, the first PEB treatment can suppress the state of the metal-containing resist film on the wafer W (e.g., the amount of water, etc.) from varying among the wafers W during the subsequent step S6.

[0127] Next, the wafer W is wet-developed using a non-polar developing material (step S6 ).

[0128] Specifically, for example, the wafer W is transported to the first developing module 30 by the transport module R2 , and a wet developing process is performed on the wafer W using a liquid non-polar developing material.

[0129] like Figure 6 As shown, the metal-containing resist film after the exposure process has an exposed region (hereinafter referred to as an aggregated region) A1 that is exposed and aggregated as described above, and an unexposed region A2 that is not exposed and is water-repellent (i.e., non-polar). In addition, the metal-containing resist film after the exposure process has an intermediate exposure region A3 that is exposed but not fully aggregated due to insufficient exposure, etc. The intermediate exposure region A3 has hydroxyl groups because the metal-containing resist is exposed but not fully aggregated, and thus becomes hydrophilic (i.e., polar).

[0130] By developing with the non-polar developing material in this step S6 , only the water-repellent unexposed region A2 in the metal-containing resist film after the exposure process is removed.

[0131] Therefore, the interface between the hydrophobic unexposed area A2 and the hydrophilic intermediate exposure area A3 becomes the surface of the pattern containing the metal resist after this step S6. Near the above-mentioned interface, most of the metal resist does not condense and has a small molecular weight. Therefore, the surface roughness of the pattern containing the metal resist after this step S6 is small.

[0132] Next, the wafer W is subjected to a second PEB process (step S7).

[0133] Specifically, for example, the wafer W is transported by the transport module R2 to the heat treatment module 40 for the second PEB treatment, and the wafer W is subjected to a heat treatment using the hot plate 41 .

[0134] In the example 1 of the processing order, the purpose of the second PEB treatment in step S7 is to further promote the aggregation reaction of the metal-containing resist and solidify the pattern of the metal-containing resist after step S6. Thus, the shape of the metal-containing resist pattern after step S6 is prevented from being damaged in the development of the subsequent step S8.

[0135] The temperature of the wafer W in the second PEB treatment is preferably 80°C to 300°C, more preferably 160°C to 250°C.

[0136] Next, the wafer W is wet-developed using a polar developing material (step S8).

[0137] Specifically, for example, the wafer W is transported to the second developing module 31 by the transport module R2 , and the wafer W is subjected to a wet developing process using a liquid polar developing material.

[0138] By developing using a polar developing material in this step S8 , the portion of the metal-containing resist pattern after step S6 that is insufficiently aggregated and has hydrophilicity is removed.

[0139] Then, the wafer W is subjected to a post-bake process (step S9).

[0140] Specifically, for example, the wafer W is transported by the transport module R2 to the heat treatment module 40 for the second PEB treatment, and the wafer W is subjected to a heating treatment using a hot plate 41 .

[0141] Then, the wafer W is carried out from the wafer processing apparatus 1 (step S10).

[0142] Specifically, the wafer W is returned to the cassette C in the reverse order of step S1.

[0143] At this point, a series of processing sequences are completed.

[0144] <Main effects of example 1 of the processing sequence>

[0145] In Example 1 of the processing sequence, a wafer W having a negative metal-containing resist film formed thereon and subjected to exposure processing and PEB processing is developed using a polar developer and a non-polar developer. Therefore, in an unexposed portion or a portion with a small exposure amount (hereinafter referred to as a low exposure portion) of the negative metal-containing resist film, a hydrophobic portion that is difficult to be removed by a polar developer can be removed by a non-polar developer, and a hydrophilic portion that is difficult to be removed by a non-polar developer can be removed by a polar developer. Therefore, according to Example 1 of the processing sequence, the amount of residue remaining on the wafer W can be reduced compared to the case where development is performed using only a non-polar developer or only a polar developer.

[0146] Furthermore, the removal performance of the hydrophobic portion by the non-polar developing material and the removal performance of the hydrophilic portion by the polar developing material are not easily affected by the temperature of the wafer W during the PEB process.

[0147] Therefore, in order to increase the exposure sensitivity of the metal-containing resist film, the temperature of the wafer W during the PEB process (specifically, the temperature during the second PEB process) can be increased.

[0148] Thus, according to Example 1 of the processing order, it is possible to simultaneously achieve an increase in the exposure sensitivity of the metal-containing resist film and a reduction in the amount of residue remaining on the wafer W during pattern formation of the metal-containing resist.

[0149] Figure 7 This is a graph showing a comparison of the thickness of the metal-containing resist film after development in the case of development with a polar developing material after development with a non-polar developing material as in Example 1 of the processing order, and in the case of development with only a non-polar developing material. In this graph, the solid line represents the former case (specifically, the case of the first PEB treatment with a chip temperature of 160°C and a heating time of 60 seconds, the development with 2-heptanone as a non-polar developing material, the second PEB treatment with a chip temperature of 220°C and a heating time of 60 seconds, the development with a tetraethylammonium hydroxide aqueous solution as a polar developing material, and the post-baking treatment with a chip temperature of 200°C and a heating time of 60 seconds). In addition, the dotted line in the figure represents the latter case (specifically, the case of the PEB treatment with a chip temperature of 180°C and a heating time of 60 seconds, the development with a mixed solution of PGMEA and acetic acid as a non-polar developing material, and the post-baking treatment with a chip temperature of 200°C and a heating time of 60 seconds).

[0150] As can be seen from the graph, when development with a polar developer is performed after development with a non-polar developer as shown in Example 1 of the processing order, a metal-containing resist film having a thickness of 10 nm or more can be obtained with a smaller exposure amount than when development with a non-polar developer is performed alone. Therefore, according to Example 1 of the processing order, the exposure sensitivity of the metal-containing resist film can be improved.

[0151] Furthermore, the inventors of the present invention also compared the number of defects when a metal-containing resist pattern with a target line width of 16 nm and a pitch of 32 nm (line and space) was formed by developing with a polar developing material after developing with a non-polar developing material as shown in Example 1 of the processing order, and developing with a non-polar developing material alone. The comparison result showed that the number of defects in the former case was about 1 / 3 of that in the latter case.

[0152] From this result and Figure 7 The results also clearly show that according to Example 1 of the processing order, it is possible to simultaneously achieve an increase in the exposure sensitivity of the metal-containing resist film and a decrease in the amount of residue remaining on the wafer W during pattern formation of the metal-containing resist.

[0153] In addition, in Example 1 of the processing order, after the development using the non-polar developing material in step S6, the surface roughness of the pattern containing the metal resist is small. In addition, the pattern containing the metal resist after the development in step S6 is solidified by the second PEB treatment in step S7. Therefore, the surface shape of the above-mentioned pattern is not easily affected by the development using the polar developing material in step S8. Therefore, the surface roughness of the pattern containing the metal resist after the development in step S8, that is, the surface roughness of the metal resist pattern finally formed, is also small.

[0154] In addition, when developing with only non-polar developer or only polar developer, the interface between the intermediate exposure area A3 and the exposure area A1 becomes the surface of the metal-containing resist pattern after development. Since the metal-containing resist is condensed near the above-mentioned interface, the molecular weight is relatively large. Therefore, the surface roughness of the metal-containing resist pattern after development is relatively large. In addition, with the condensation reaction, the fluctuation of chemical concentration will accumulate statistically. Therefore, in the case of development using the condensation amount of the metal complex, such as development with only non-polar developer or only polar developer, the surface roughness tends to be larger than the development on the surface with non-condensed polarity change, such as development with non-polar developer in Example 1 of the processing order.

[0155] In addition, the metal-containing resist film absorbs energy due to exposure on the surface side, that is, the upper part, so Figure 6 As shown, the lower part of the condensation region A1 is narrower than the upper part, that is, the condensation region A1 has a shape that tapers downward. Therefore, if the development is simply performed, the pattern containing the metal resist will also have a shape that tapers downward when observed in cross section. At this time, especially when the pattern is a columnar pattern, there is a risk of pattern collapse.

[0156] In contrast, in Example 1 of the processing order, by using a developing material with a lower polarity (e.g., butyl acetate) as a non-polar developing material during development in step S6, it is possible to suppress the metal-containing resist pattern after step S6 from being tapered downward. As a result, it is possible to suppress the metal-containing resist pattern shape after development in step S8, i.e., the metal-containing resist pattern finally formed from being tapered downward. Therefore, according to Example 1 of the processing order, pattern collapse can be suppressed.

[0157] In addition, the reason for the pattern collapse is considered to be as follows: that is, there is a portion having a ligand and maintaining water repellency on the lower surface of the condensation region A1 and the intermediate exposure region A3. Therefore, the developer with low polarity penetrates between the lower surface of the condensation region A1 and the intermediate exposure region A3 and the surface of the wafer W, resulting in the collapse of the metal-containing resist pattern after development using the developer with low polarity.

[0158] In contrast, in Example 1 of the processing order, a method can be adopted in which the exposure amount during the exposure process is increased to make the metal-containing resist pattern after development with a non-polar developing material in step S6 coarser, and then the pattern is made thinner during development with a polar developing material in step S8. This method can suppress pattern collapse.

[0159] <Variation 1 of Example 1 of Processing Order>

[0160] Figure 8 This is a flowchart showing main steps of Modification 1 of Example 1 of the processing procedure.

[0161] In the example 1 of the processing order, the PEB process is performed twice. However, in the present modification 1, the second PEB process is omitted, that is, the PEB process between the development of the non-polar developing material in step S6 and the development of the polar developing material in step S8 is omitted.

[0162] Specifically, in this modification example 1, after the exposure process PEB process of step S4 in example 1 of the processing order is completed, the only PEB process in this processing order is executed (step S5a).

[0163] Next, the development using the non-polar development material of step S6 in the example 1 of the processing sequence (hereinafter referred to as "non-polar development") is performed. Next, the development using the polar development material of step S8 in the example 1 of the processing sequence (hereinafter referred to as "polar development") is performed without the PEB process in between. Thereafter, step S9 and subsequent steps in the example 1 of the processing sequence are performed.

[0164] The temperature of the PEB treatment in step S5a may be the same as that of the first PEB treatment in step S5 in treatment order example 1. In addition, the temperature of the PEB treatment in step S5a may also be in a higher temperature range than that of the first PEB treatment, for example, 180°C to 220°C.

[0165] By setting the temperature to 180° C. or higher, it is possible to suppress the non-polar developing material from penetrating between the lower surface of the condensation area A1 and the intermediate exposure area A3 and the surface of the wafer W during the non-polar development in step S8. Therefore, it is possible to suppress pattern collapse. In addition, by setting the temperature to 220° C. or lower, the amount of residue remaining on the wafer W can be more reliably reduced.

[0166] <Main Effects of Modification 1 of Processing Order Example 1>

[0167] According to the present modification example 1, for the same reasons as in the example 1 of the processing order, it is possible to simultaneously achieve an increase in the exposure sensitivity of the metal-containing resist film and a reduction in the amount of residue remaining on the wafer W during pattern formation of the metal-containing resist.

[0168] In addition, the present modification example 1 can achieve high throughput because the number of steps is small compared to the process order example 1. Furthermore, since the heat treatment module 40 for PEB treatment between non-polar development and polar development is not required, the cost can be reduced.

[0169] Fig. 9 This is a graph comparing the thickness of the metal-containing resist film after development when development is performed as in Modification 1 of Example 1 according to the processing order and when only non-polar development is performed. In the graph, the solid line represents the former (specifically, PEB treatment with a chip temperature of 210°C and a heating time of 60 seconds, non-polar development using a mixture of PGMEA and acetic acid, and polar development using an aqueous solution of tetraethylammonium hydroxide are performed in sequence). In addition, in the graph, the dotted line represents the latter (specifically, PEB treatment with a chip temperature of 180°C and a heating time of 60 seconds, and non-polar development using a mixture of PGMEA and acetic acid are performed in sequence).

[0170] As is clear from the figure, when the PEB treatment between the non-polar development and the polar development is omitted as shown in the modification 1 of the processing order example 1, a metal-containing resist film having a thickness of 10 nm or more can be obtained with a smaller exposure amount than when only the non-polar development is performed as in the processing order example 1. Thus, according to the modification 1 of the processing order example 1, the exposure sensitivity of the metal-containing resist film can be increased.

[0171] Fig.10 It is a graph showing the relationship between the CD (Critical Dimension) (specifically, the hole diameter of a hole pattern with a pitch of 32 nm) of a metal-containing resist pattern after development and the exposure amount. Fig.11 It is a diagram showing the relationship between the CD and the roughness of the pattern (uLCDU: Unbiased Local Critical Dimension Uniformity). Fig.12 is a graph showing the relationship between the above CD and the defect ratio. Figure 10 to Figure 12In the figure, the solid line indicates the case where development is performed as in the variant example 1 of the processing order (specifically, PEB treatment with a chip temperature of 215°C and a heating time of 60 seconds, non-polar development using a mixture of PGMEA and acetic acid, and polar development using an aqueous solution of tetraethylammonium hydroxide are performed in sequence). In addition, the dotted line indicates the case where development is performed as in the processing order example 1 (specifically, PEB treatment with a chip temperature of 200°C and a heating time of 60 seconds, non-polar development using a mixture of PGMEA and acetic acid, PEB treatment with a chip temperature of 190°C and a heating time of 60 seconds, and polar development using an aqueous solution of tetraethylammonium hydroxide as a polar developing material are performed in sequence). Furthermore, the dotted line indicates the case where only non-polar development is performed (specifically, PEB treatment with a chip temperature of 180°C and a heating time of 60 seconds, and non-polar development using a mixture of PGMEA and acetic acid are performed in sequence).

[0172] from Fig.10 As is clear from the graph, when both non-polar development and polar development are performed according to Example 1 of the processing order and its Modified Example 1, the CD change relative to the exposure change is smaller than when only non-polar development is performed, that is, the exposure margin of CD is higher. In particular, when the PEB process is omitted between the non-polar development and the polar development as in Modified Example 1 of Example 1 of the processing order, the exposure margin of CD is higher.

[0173] In addition, from Fig.11 It can be clearly seen from the figure that when both non-polar development and polar development are performed as in Example 1 of the processing order and its modified example 1, the roughness of the pattern surface is smaller in the CD range below 18nm than when only non-polar development is performed.

[0174] Furthermore, from Fig.12 As is clear from the figure, when both non-polar development and polar development are performed as in Example 1 of the processing order and its Modified Example 1, the CD range of 20 nm or less where the defect ratio is 0 is wider than that in the case where only non-polar development is performed. Therefore, according to Modified Example 1 of Example 1 of the processing order, the amount of residue remaining on the wafer W when the pattern containing the metal resist is formed can be reduced, similarly to Example 1 of the processing order.

[0175] <Example of Development Module Used in Modification 1 of Example 1 of Processing Order>

[0176] In the case where polar development is performed after nonpolar development as in Modification 1 of Process Order Example 1, both nonpolar development and polar development can be performed in one development module. By performing both nonpolar development and polar development in the same development module, high production quantization and low cost can be achieved.

[0177] Fig.13 This is a diagram showing an example of the structure of a developing module that performs both non-polar development and polar development.

[0178] Fig.13 The developing module 34 is provided with a rotary chuck 140 for holding the wafer W and rotating it around a vertical axis. The rotary chuck 140 is rotatable and can be raised and lowered.

[0179] A cup-shaped body 150 is provided so as to surround the wafer W held by the spin chuck 140. The cup-shaped body 150 is used to receive and recover the liquid scattered or dropped from the wafer W. The detailed structure of the cup-shaped body 150 will be described later.

[0180] Furthermore, the developing module 34 is provided with nozzles 160 and 161 .

[0181] The nozzle 160 is used to discharge the non-polar developing material. Specifically, the nozzle 160 discharges the non-polar developing material toward the wafer W held by the spin chuck 140 .

[0182] The nozzle 161 is used to discharge the polarity developing material. Specifically, the nozzle 161 discharges the polarity developing material toward the wafer W held by the spin chuck 140 .

[0183] These nozzles 160 and 161 are provided so as to be movable in the horizontal direction and to be able to be raised and lowered.

[0184] The cup-shaped body 150 includes a cup main body 151 and a movable cup 152 that can be raised and lowered relative to the cup main body 151 .

[0185] The cup body 151 includes a cup base 153 and a fixed cup 154 ​​fixed to the cup base 153 .

[0186] The cup base 153 has an annular outer peripheral wall 153a and an annular inner peripheral wall 153b, and the outer peripheral wall 153a and the inner peripheral wall 153b extend in the up-down direction (vertical direction). The inner diameter of the outer peripheral wall 153a is larger than the diameter of the wafer W, the outer diameter of the inner peripheral wall 153b is smaller than the diameter of the wafer W, and the height of the inner peripheral wall 153b is lower than the height of the outer peripheral wall 153a.

[0187] In addition, the cup base 153 has a bottom wall 153c connecting the lower end of the outer peripheral wall 153a and the lower end of the inner peripheral wall 153b, and an upper wall 153d extending from the upper end of the outer peripheral wall 153a toward the inner peripheral direction, and the upper side of the inner peripheral wall 153b is open. A protrusion 153e extending toward the inner peripheral direction is provided at the upper end of the inner peripheral wall 153b, and the cup base 153 can be fixed by clamping the protrusion 153e between the fixing cup 154 ​​and the retaining plate 155.

[0188] The fixing cup 154 ​​constitutes an annular internal structure located between the outer peripheral wall 153a and the inner peripheral wall 153b. The fixing cup 154 ​​has an annular peripheral wall 154a located between the outer peripheral wall 153a and the inner peripheral wall 153b.

[0189] The movable cup 152 is an annular member disposed between the outer peripheral wall 153a of the cup base 153 and the fixed cup 154 ​​so as to be movable up and down, and has a distribution portion 152a at the upper end and a peripheral wall 152b at the lower side of the distribution portion 152a. The distribution portion 152a is used to discharge the non-polar developer and the polar developer separately, and its upper surface is formed by an inclined surface 152c that gradually becomes lower as it goes to the outer peripheral side.

[0190] The peripheral wall 152b is formed in an annular shape, and its inner diameter is larger than the outer diameter of the peripheral wall 154a of the fixed cup 154, and its outer diameter is smaller than the inner diameter of the outer peripheral wall 153a of the cup base 153. In addition, the outer peripheral end of the inclined surface 152c of the distribution part 152a is connected to the outer peripheral surface of the peripheral wall 152b.

[0191] On the bottom wall 153 c of the cup base 153 , two partition walls 153 f and 153 g formed in an annular shape are formed between the outer peripheral wall 153 a and the inner peripheral wall 153 b .

[0192] In addition, the bottom wall 153c is formed with a first recovery port 153h for recovering non-polar developer between the outer peripheral wall 153a and the partition wall 153f on the outer peripheral side. Furthermore, the bottom wall 153c is formed with a second recovery port 153i for recovering polar developer between the partition walls 153f and 153g, and a mist recovery port 153j for recovering atomized developer is formed between the partition wall 153g on the inner peripheral side and the inner peripheral wall 153b.

[0193] When developing with a non-polar developing material is performed, the movable cup 152 is lowered and the non-polar developing material is discharged from the nozzle 161 .

[0194] In addition, the pump connected to the first recovery port 153h is driven, so that the non-polar developer scattered by the rotation of the wafer W and the non-polar developer flowing into the lower side of the wafer W and falling can be guided from between the distribution portion 152a of the movable cup 152 and the outer peripheral wall 153a of the cup base 153 to the first recovery port 153h, and recovered through the recovery port 153h.

[0195] On the other hand, when development using a polar developing material is performed, the movable cup 152 rises and the polar developing material is discharged from the nozzle 162 .

[0196] In addition, the pump connected to the second recovery port 153i is driven, so that the polar developing material scattered approximately horizontally by the rotation of the wafer W can be guided from between the distribution portion 152a of the movable cup 152 and the fixed cup 154 ​​to the second recovery port 153i and recovered through the recovery port 153i.

[0197] Thus, according to Fig.13 The developing module 34 can recover the non-polar developing material and the polar developing material separately.

[0198] <Other Modifications of Example 1 of Processing Order>

[0199] In the above-mentioned modification 1, the second PEB process performed between the polar development and the non-polar development in the example 1 of the process order is omitted. However, instead of this, the first PEB process performed before the polar development may be omitted.

[0200] <Processing order example 2>

[0201] Fig.14 This is a flowchart showing the main steps of Example 2 of the processing sequence.

[0202] In the processing order example 2, if Fig.14 As shown, after the steps up to the first PEB process of step S5 in example 1 of the processing order are performed, the entire surface of the wafer W is irradiated with ultraviolet rays (step S21).

[0203] Specifically, the wafer W is transported to the ultraviolet irradiation module 45 by the transport module R2, and ultraviolet rays are irradiated to the entire surface of the wafer W. At this time, the irradiation amount of ultraviolet rays may be uniform within the surface of the wafer W, or may be different within the surface of the wafer W.

[0204] Thereafter, step S6 and subsequent steps in example 1 of the processing order are executed.

[0205] <Main effects of example 2 of the processing order>

[0206] In the example 2 of the processing sequence, similarly to the example 1 of the processing sequence, since development is performed using a polar developing material and a non-polar developing material, the amount of residue remaining on the wafer W can be reduced.

[0207] Furthermore, the removal performance of the non-polar developing material on the water-repellent portion and the removal performance of the polar developing material on the hydrophilic portion are not easily negatively affected by the ultraviolet irradiation in step S21.

[0208] Furthermore, the ultraviolet irradiation in step S21 can increase the exposure sensitivity of the metal-containing resist film.

[0209] Therefore, according to Example 2 of the processing order, it is possible to simultaneously achieve an increase in the exposure sensitivity of the metal-containing resist film and a decrease in the amount of residue remaining on the wafer W when the metal-containing resist is patterned.

[0210] In addition, in Example 2 of the processing order, similarly to Example 1 of the processing order, the surface roughness of the metal-containing resist pattern finally formed can be reduced, and pattern collapse can be suppressed.

[0211] <Variations 1 and 2 of Example 2 of Processing Order>

[0212] Fig.15 This is a flowchart showing main steps of Modification Example 1 of Example 2 of the processing order. Fig.16 This is a flowchart of main steps of Modification Example 2 of Example 2 showing the processing order.

[0213] In Example 2 of the processing order, the ultraviolet irradiation of the entire surface of the wafer W in step S21 is performed after the first PEB treatment in step S5 and before the development of the non-polar developing material in step S6, but the execution timing of step S21 is not limited to this.

[0214] The ultraviolet irradiation of the entire surface of the wafer W in step S21 may be performed as follows, for example. Fig.15 As shown, after the exposure process and before the first PEB process, or as Fig.16 As shown, it is performed before the exposure process. Specifically, it can be performed after the PAB process and before the exposure process.

[0215] However, in order to reduce the amount of residue remaining on the wafer W, the timing of executing the ultraviolet irradiation on the entire surface of the wafer W in step S21 is preferably after the first PEB treatment in step S5 and before the development of the non-polar developing material in step S6. In addition, in order to increase the difference in dissolution rate between the portion removed by the development of the polar developing material and the portion not removed, that is, the dissolution contrast, this timing is also preferred.

[0216] <Variation 3 of Example 2 of Processing Order>

[0217] In Example 2 of the processing order, the PEB treatment is performed twice, but the first PEB treatment performed before the development of the non-polar developing material in step S6 can be omitted.

[0218] <Processing order example 3>

[0219] Fig.17 This is a flowchart showing the main steps of Example 3 of the processing sequence.

[0220] In the processing order example 1, the non-polar developing material is developed first, and then the polar developing material is developed. Fig.17As shown, the development of the polar developing material is performed first (step S8), and then the development of the non-polar developing material is performed (step S6).

[0221] Specifically, for example, after the steps up to the first PEB process of step S5 in example 1 of the processing order are completed, wet development is performed using a polar developing material (step S8).

[0222] Next, after the second PEB process of step S7 in example 1 of the process order is performed, wet development is performed using a non-polar developing material (step S6).

[0223] Thereafter, the wafer W is subjected to a post-bake process (step S9), and the wafer W is carried out from the wafer processing apparatus 1 (step S10).

[0224] <Main effects of example 3 of the processing order>

[0225] According to the processing order example 3, for the same reason as the processing order example 1, it is possible to simultaneously achieve an increase in the exposure sensitivity of the metal-containing resist film and a reduction in the amount of residue remaining on the wafer W during pattern formation of the metal-containing resist.

[0226] Fig.18 This is a diagram for explaining why pattern collapse can be suppressed according to Example 3 of the processing order.

[0227] In addition, in Example 3 of the processing order, if Fig.18 As shown, in the metal-containing resist after the development of the polar developer material previously performed, the lower part of the intermediate exposure area A3 located on the side of the condensation area A1 can remain. The lower part of the intermediate exposure area A3 located on the side of the condensation area A1 (the light gray part in the figure) can be insoluble in the non-polar developer material used in the subsequent development through the second PEB treatment. As a result, the shape of the metal-containing resist pattern after the development of the non-polar developer material in step S6, that is, the metal-containing resist pattern finally formed, can be suppressed from becoming a downwardly tapered shape. Therefore, according to Example 3 of the processing order, pattern collapse can be suppressed.

[0228] Furthermore, in the example 3 of the processing sequence, the second PEB processing after the development with the polar developer can improve the adhesion between the lower surface of the condensed area A1 and the surface of the wafer W. Therefore, it is possible to suppress the penetration of the developer with low polarity between the lower surface of the hydrophobic condensed area A1 and the surface of the wafer W to cause pattern collapse.

[0229] <Variation of Example 3 of Processing Order>

[0230] When development with a polar developing material is performed first and development with a non-polar developing material is performed later as in Example 3 of the processing sequence, the entire surface of the wafer W may be irradiated with ultraviolet rays as in Example 2 of the processing sequence.

[0231] In this case, the timing of ultraviolet irradiation on the entire surface of the wafer W may be, for example, after the first PEB treatment in step S5 and before the development of the non-polar developing material in step S8, as in Example 2 of the processing order. In addition, the timing of ultraviolet irradiation on the entire surface of the wafer W may be after the exposure treatment and before the first PEB treatment, as in Modification 1 of Example 2 of the processing order, or before the exposure treatment, as in Modification 2 of Example 2 of the processing order.

[0232] <Processing order example 4>

[0233] Fig.19 This is a flowchart showing the main steps of Example 4 of the processing sequence.

[0234] In the processing order examples 1 to 3, the development of the non-polar developing material and the development of the polar developing material are performed respectively. Fig.19 As shown, development is performed using a mixture of a non-polar developing material and a polar developing material, that is, a mixed developing material.

[0235] Specifically, for example, after the steps up to the exposure process of step S4 in the example 1 of the processing order are performed, the PEB process is performed on the wafer W (step S31).

[0236] More specifically, for example, the wafer W is transported to the heat treatment module 40 for PEB treatment of the mixed developer material by the transport module R2 , and the wafer W is subjected to heat treatment by the hot plate 41 .

[0237] Next, wet development is performed using the mixed developing material (step S32 ).

[0238] Specifically, for example, the wafer W is transported to the third developing module 32 by the transport module R2, and the wafer W is subjected to a wet developing process using the liquid mixed developing material.

[0239] Thereafter, the wafer W is subjected to a post-bake process (step S9), and the wafer W is carried out from the wafer processing apparatus 1 (step S10).

[0240] <Main effects of example 4 of the processing order>

[0241] According to the processing order example 4, for the same reason as the processing order example 1, it is possible to simultaneously achieve an increase in the exposure sensitivity of the metal-containing resist film and a reduction in the amount of residue remaining on the wafer W during pattern formation of the metal-containing resist.

[0242] <Variation of Example 4 of Processing Order>

[0243] When developing using a mixed developing material which is a mixture of a non-polar developing material and a polar developing material as in Example 4 of the processing sequence, the entire surface of the wafer W may be irradiated with ultraviolet rays as in Example 2 of the processing sequence.

[0244] In this case, the timing of ultraviolet irradiation on the entire surface of the wafer W is, for example, after the PEB treatment in step S31 and before the development of the mixed developing material in step S32, similar to the example 2 of the processing order. In addition, the timing of ultraviolet irradiation on the entire surface of the wafer W may be after the exposure treatment and before the PEB treatment, similar to the modification 1 of the example 2 of the processing order, or before the exposure treatment, similar to the modification 2 of the example 2 of the processing order.

[0245] <Processing order example 5>

[0246] Fig. 20 This is a flowchart showing the main steps of Example 5 of the processing sequence.

[0247] In the processing order example 5, if Fig. 20 As shown, after the steps up to the exposure process of step S4 in the example 1 of the processing order are performed, the PEB process is performed on the wafer W (step S41).

[0248] Specifically, the wafer W is transported by the transport module R2 to the heat treatment module 40 for PEB treatment in Example 5 of the process sequence, and the wafer W is subjected to heat treatment using the hot plate 41 .

[0249] Next, the entire surface of the wafer W is irradiated with ultraviolet rays (step S21).

[0250] Specifically, the wafer W is transported to the ultraviolet irradiation module 45 by the transport module R2, and ultraviolet rays are irradiated to the entire surface of the wafer W. At this time, the irradiation amount of ultraviolet rays may be uniform within the surface of the wafer W, or may be different within the surface of the wafer W.

[0251] By the ultraviolet irradiation, the ligands of the metal-containing resist are detached in the water-repellent unexposed region A2, and the hydroxyl groups are bonded to the detached portions, so that the unexposed region A2 is hydrophilized and becomes soluble in the polar developing material.

[0252] Next, the wafer W is wet developed using a polar developing material (step S8).

[0253] The unexposed area A2 also becomes hydrophilic through ultraviolet irradiation in step S21, so that by developing with a polar developing material in step S8, not only the hydrophobic intermediate exposure area A3 in the metal-containing resist film after exposure and PEB treatment but also the unexposed area A2 can be removed.

[0254] Thereafter, the wafer W is subjected to a post-bake process (step S9), and the wafer W is carried out from the wafer processing apparatus 1 (step S10).

[0255] Wherein, the wavelength of the ultraviolet rays irradiated in step S21 is, for example, more than 10nm, and when wet development is performed in this example, it is preferably more than 160nm. By being configured to be more than 160nm, ozone will not be generated even if ultraviolet rays are irradiated in the atmosphere, thereby being able to suppress the influence of ozone on development. In addition, the wavelength of the ultraviolet rays irradiated in step S21 is, for example, less than 400nm, and preferably less than 300nm. By being configured to be less than 300nm, the metal-containing resist film can efficiently absorb ultraviolet rays.

[0256] <Main effects of example 5 of the processing order>

[0257] In Example 5 of the processing sequence, the following processes are performed: a process of irradiating the entire surface of a chip W on which a negative metal-containing resist film is formed, with ultraviolet rays in addition to the exposure process; and a process of developing the chip W on which a negative metal-containing resist film is formed, which has been subjected to the exposure process and the PEB process and the above-mentioned ultraviolet irradiation process, using a polar developing material.

[0258] That is, in the example 5 of the processing sequence, the hydrophobic unexposed area which is difficult to be removed by the polar developer is hydrophilized by the above-mentioned ultraviolet irradiation step, and then the polar developer is developed. Therefore, in the metal-containing resist film after the exposure process and the PEB process, both the unexposed area A2 and the intermediate exposure area A3 are appropriately removed. Therefore, according to the example 1 of the processing sequence, the amount of residue remaining on the wafer W can be reduced compared with the case of developing only with the polar developer.

[0259] Furthermore, the removal performance of the polar developing material on the hydrophilic portion is not easily affected by the temperature of the wafer W during the PEB process.

[0260] Therefore, in order to increase the exposure sensitivity of the metal-containing resist film, the temperature of the wafer W during the PEB process can be increased, and the condensation region A1 can be pushed outward within a range that does not affect the CD.

[0261] Therefore, according to Example 5 of the processing order, it is possible to simultaneously achieve an increase in the exposure sensitivity of the metal-containing resist film and a reduction in the amount of residue remaining on the wafer W when the metal-containing resist is patterned.

[0262] Fig.21 This is a graph (curve chart) comparing the thickness of the metal-containing resist film after development when ultraviolet irradiation and development with a polar developer are performed as in Example 5 of the processing sequence and when development with a non-polar developer is performed without ultraviolet irradiation. In the graph, the solid line, dotted line, and dashed line represent the former (specifically, PEB treatment with a wafer temperature of 180°C (dash-dot line), 200°C (dotted line), or 220°C (solid line) and a heating time of 60 seconds, and an irradiation dose of 40 mJ / cm 2 In addition, the dotted line in the graph represents the latter case (specifically, a PEB treatment at a chip temperature of 180°C and a heating time of 60 seconds, a development using a mixed solution of PGMEA and acetic acid as a non-polar developing material, and a post-baking treatment at a chip temperature of 200°C and a heating time of 60 seconds were performed in sequence).

[0263] As is clear from the graph, when ultraviolet irradiation and development with a polar developer are performed as shown in Example 5 of the processing order, a metal-containing resist film having a thickness of 10 nm or more can be obtained with a smaller exposure amount during the exposure process than when development with a non-polar developer is performed without ultraviolet irradiation. Thus, according to Example 5 of the processing order, the exposure sensitivity of the metal-containing resist film can be increased.

[0264] Furthermore, it is clear from the graph that when development is performed as shown in Example 5 of the processing order, even if the wafer temperature during the PEB process is increased, no metal-containing resist remains in the low-exposure region, that is, no residue is generated.

[0265] In addition, the inventors of the present invention also compared the number of defects when forming a metal-containing resist pattern with a target line width of 16 nm and a pitch of 32 nm (line and space) in the case of ultraviolet irradiation and development with a polar developer as shown in Example 5 of the processing order and in the case of development with a non-polar developer without ultraviolet irradiation. The comparison results showed that the number of defects in the former case was reduced by about 40% compared with the latter.

[0266] From this result and Fig.21As can be seen from the results, according to Example 5 of the processing order, it is possible to simultaneously achieve an increase in the exposure sensitivity of the metal-containing resist film and a decrease in the amount of residue remaining on the wafer W when the metal-containing resist pattern is formed.

[0267] In addition, in Example 5 of the processing order, the difference in dissolution rate (dissolution contrast) between the portion removed by the development of the polar developer and the portion not removed in the metal-containing resist film increases by ultraviolet irradiation. The surface roughness of the metal-containing resist pattern formed by the development of the polar developer is inversely proportional to the contrast of the dissolution rate. Therefore, according to Example 5 of the processing order, the roughness of the surface of the metal-containing resist pattern after development can be reduced.

[0268] Furthermore, since the developer is a polar developer, the developer is unlikely to penetrate between the lower surface of the water-repellent aggregation region A1 and the surface of the wafer W. Therefore, according to the example 5 of the processing sequence, pattern collapse can be suppressed.

[0269] In addition, in Example 5 of the processing sequence, ultraviolet irradiation and polarity development are performed using the wafer processing device 1, and there is no need to send the wafer W to be processed from the wafer processing device 1. That is, ultraviolet irradiation and polarity development are performed inline (continuously on the production line). Therefore, the time from the end of ultraviolet irradiation to the start of polarity development is short, for example, within 10 minutes. Therefore, the influence of the atmosphere around the wafer W on the polarity development between the end of ultraviolet irradiation and the start of polarity development can be suppressed.

[0270] Fig. 22 This is a graph showing the relationship between CD (specifically, line width) and exposure dose when a metal-containing resist pattern having a target line width of 16 nm and a pitch of 32 nm (line and space) is formed. Fig.23 It is a graph showing the relationship between the CD and the roughness (uLWR: Unbiased Line Width Roughness) of the pattern. Fig.24 is a graph showing the relationship between the above CD and the defect ratio. Figure 22 to Figure 24 In the figure, the solid line indicates the case where the development was performed as in Example 5 of the processing sequence (specifically, the PEB treatment was performed in sequence with a wafer temperature of 200° C. and a heating time of 60 seconds, a wavelength of 248 nm and an irradiation amount of 70 mJ / cm 2 In addition, the dotted line indicates the case where only non-polar development is performed without ultraviolet irradiation (specifically, the case where PEB treatment with a chip temperature of 180°C and a heating time of 60 seconds and non-polar development using a mixed solution of PGMEA and acetic acid are performed in sequence).

[0271] from Fig. 22 It is clear from the graph that when ultraviolet irradiation and polar development are performed in sequence as shown in Example 5 of the processing order, the CD change relative to the exposure change is smaller than when non-polar development is performed without ultraviolet irradiation, that is, the exposure margin of CD is higher.

[0272] In addition, from Fig.23 It is clear from the graph that when ultraviolet irradiation and polar development are performed in sequence as shown in Example 5 of the processing order, the roughness of the pattern surface is smaller within the CD range of less than 20 nm, compared with the case where non-polar development is performed without ultraviolet irradiation.

[0273] In addition, from Fig.24 As can be clearly seen from the graph, when ultraviolet irradiation and polar development are performed as shown in Example 5 of the processing order, the CD range below 19 nm where the defect ratio is 0 is wider than the case where non-polar development is performed without ultraviolet irradiation.

[0274] Fig.25 This is a graph showing the relationship between CD (specifically, column width) and exposure dose when a columnar metal-containing resist pattern with a target width of 18 nm is formed. Fig.26 It is a graph showing the relationship between the CD and the roughness (uLCDU) of the pattern. Fig. 27 is a graph showing the relationship between the above CD and the defect ratio. Figure 25 to Figure 27 In the figure, the solid line indicates the case where the development was performed as in Example 5 of the processing sequence (specifically, the PEB treatment was performed in sequence with a wafer temperature of 160° C. and a heating time of 60 seconds, a wavelength of 248 nm and an irradiation amount of 50 mJ / cm 2 In addition, the dotted line indicates the case where no ultraviolet irradiation was performed and only non-polar development was performed (specifically, PEB treatment with a chip temperature of 160° C. and a heating time of 60 seconds and non-polar development using a mixed solution of PGMEA and acetic acid were performed in sequence).

[0275] from Fig.25 As can be clearly seen from the graph, when ultraviolet irradiation and polar development were performed in sequence and deionized water was used as shown in Example 5 of the processing order, the CD change relative to the exposure change was smaller than the case where non-polar development was performed without ultraviolet irradiation, that is, the exposure margin of CD was higher. Specifically, the exposure margin was improved by 55%.

[0276] In addition, from Fig.26It can be clearly seen from the chart that when ultraviolet irradiation and polar development are performed in sequence and deionized water is used as shown in Example 5 of the processing order, the roughness of the pattern surface is smaller within the CD range of less than 20 nm, compared with the case where non-polar development is performed without ultraviolet irradiation.

[0277] Furthermore, from Fig. 27 It is clear from the chart that when ultraviolet irradiation and polar development are performed in sequence and deionized water is used as shown in Example 5 of the processing order, the CD range below 19nm with a defect ratio of 0 is wider than when non-polar development is performed without ultraviolet irradiation. Specifically, when non-polar development is performed without ultraviolet irradiation, pattern collapse occurs in columnar patterns with a CD of less than 17nm. In contrast, when ultraviolet irradiation and polar development are performed in sequence and deionized water is used as shown in Example 5 of the processing order, pattern collapse does not occur even in columnar patterns with a CD of 15nm. This is because deionized water as a developer does not easily penetrate into the lower surface of the resist (water repellency), thereby reducing the occurrence of pattern collapse.

[0278] Among them, using an aqueous developing material such as deionized water as a non-polar developing material can suppress the influence on the environment more than using a tetraethylammonium hydroxide aqueous solution.

[0279] <Variations 1 and 2 of Example 5 of Processing Order>

[0280] Fig.28 This is a flowchart of main steps of Modification Example 1 of Example 5 showing the processing order. Fig.29 This is a flowchart of the main steps of the second variant of the fifth example showing the processing order.

[0281] In the processing order example 5, the ultraviolet irradiation of the entire surface of the wafer W in step S21 is performed after the PEB treatment in step S41 and before the development of the polar developing material in step S8, but the execution timing of step S21 is not limited to this.

[0282] The ultraviolet irradiation of the entire surface of the wafer W in step S21 can be performed as follows, for example. Fig.28 As shown, after the exposure process and before the PEB process, or as Fig.29 As shown, it is performed before the exposure treatment. Specifically, it can be performed after the PAB treatment and before the exposure treatment.

[0283] However, in order to reduce the amount of residue remaining on the wafer W, the timing of executing the ultraviolet irradiation on the entire surface of the wafer W in step S21 is preferably after the PEB treatment in step S41 and before the development of the polar developing material in step S8. In addition, in order to increase the difference in dissolution rate between the portion removed by the development of the polar developing material and the portion not removed, that is, the dissolution contrast, this timing is preferred.

[0284] <Variation 3 of Example 5 of Processing Order>

[0285] Fig.30 This is a flowchart of the main steps of Modification Example 3 of Example 5 showing the processing order.

[0286] In this modification 3, at the same time as or after the polarity development in step S8 after the ultraviolet irradiation in step S21, the peripheral portion of the wafer W is cleaned using the polarity cleaning liquid by the second developing module 31 without moving the wafer W (step S51). That is, the polarity development in step S8 and the polarity cleaning of the peripheral portion of the wafer W share the same developing module, specifically, the cup-shaped body (not shown) for recovering the processing liquid applied to the wafer W. Therefore, the number of modules mounted in the wet processing unit 2 can be reduced, thereby realizing a small footprint (occupied area) of the wet processing unit 2.

[0287] When the metal-containing resist is developed, metal may remain on the periphery of the wafer. As a method for removing the metal, for example, a method of using a cleaning solution with a higher acid concentration than the developer or a method of supplying a solvent in the developer as the cleaning solution can be considered. However, the cleaning solution of the former method is expensive. In addition, in the latter method, it is difficult to remove the above-mentioned metal unless a large amount of cleaning solution is used.

[0288] In this modification 3, metal may remain on the periphery of the wafer after development. However, in this modification 3, since ultraviolet irradiation is performed before development and polar cleaning of the periphery of the wafer W, the resist film on the periphery of the wafer W is hydrophilized, and thus the metal can be removed in the form of a hydrophilized substance using a relatively inexpensive polar cleaning liquid such as an aqueous cleaning liquid. Furthermore, since the hydrophilized substance is easily washed away by the polar cleaning liquid, the consumption of the cleaning liquid required to remove the metal can be reduced.

[0289] In addition, by making the developing material used for polar development the same as the cleaning liquid used for cleaning the periphery of the wafer, or by using an aqueous cleaning liquid, the developing material and the cleaning liquid recovered in the cup-shaped body in the developing module can be discharged through the same waste liquid pipeline.

[0290] Furthermore, in this modification 3, during the ultraviolet irradiation, the ultraviolet irradiation may be performed on the bevel of the wafer W. Thus, the resist film on the bevel can be hydrophilized, and when the peripheral portion of the wafer W is polarized and cleaned, metal residue on the bevel can be further suppressed.

[0291] In addition, in the present modification example 3, after step S51, step S9 and subsequent steps in the processing order example 1 are executed.

[0292] The above description describes the cleaning of the peripheral portion of the wafer W with a polar cleaning liquid, but the peripheral portion of the wafer W may be first cleaned with a non-polar cleaning liquid and then cleaned with a polar cleaning liquid. In addition, the peripheral portion of the wafer W may be cleaned with a mixture of a polar cleaning liquid and a non-polar cleaning liquid.

[0293] In addition, the cleaning target may be only the front side of the peripheral portion of the wafer W, or both the front side and the back side of the peripheral portion of the wafer W.

[0294] Furthermore, the cleaning object is not limited to the peripheral portion of the wafer W, but may also be the entire back side of the wafer W.

[0295] Furthermore, the cleaning material used for cleaning the wafer W is not limited to the polar cleaning solution, that is, not limited to the polar liquid, but may be a polar gas. As the polar gas of the cleaning material, for example, the same gas as that used for dry developing can be used.

[0296] <Other Modifications of Examples 1 to 5 of Processing Procedure>

[0297] In the above-mentioned processing sequence examples 1 to 5 and their variations, the development performed is wet development, but part or all of the development in each processing sequence may be dry development. When dry development is performed, dry development modules 121 to 123 may be used depending on the type of developing material used in the development.

[0298] In addition, when dry development is performed, the heat treatment module 124 may perform a heating treatment on the wafer W before and after the dry development.

[0299] In addition, dry development may be performed outside the wafer processing apparatus 1. However, including Example 5 of the processing sequence, it is preferred that the dry development and other steps constituting each processing sequence are all performed in the wafer processing apparatus 1, that is, inline. This is because the time until the start of dry development can be shortened, and as a result, the influence of the atmosphere around the wafer W before the start of dry development on the dry development can be suppressed.

[0300] In addition, in Example 5 of the processing sequence, when the polarity development is performed by dry development, i.e., using gas under reduced pressure, the ultraviolet irradiation treatment can also be performed under reduced pressure. In this case, the ultraviolet irradiation can be vacuum ultraviolet, i.e., its wavelength can be, for example, 10nm to 200nm or less. When the ultraviolet irradiation treatment is performed under reduced pressure, the plasma generated in the module performing the dry development can be used as the light source of the ultraviolet.

[0301] In addition, the above dry development is a method of using gas under reduced pressure, but it can also be a method of using gas under atmospheric pressure. When developing with gas under atmospheric pressure, it is possible to set a development processing module in the wet processing unit 2 of atmospheric atmosphere instead of the dry processing unit 3 of reduced pressure atmosphere.

[0302] Not only in the example 5 of the processing order, but also in the examples 1 to 4 of the processing order, the wafer W may be cleaned during development or immediately after development (ie, immediately after development).

[0303] Cleaning of the wafer W is not limited to being performed during or immediately after development. Since the wafer W may be contaminated by metal after resist film formation, heat treatment, or exposure, the wafer W may be cleaned after at least any of these treatments.

[0304] In addition, the wafer W may be cleaned after ultraviolet irradiation is performed only on the portion (the front peripheral portion of the wafer W, the back peripheral portion of the wafer W, the entire back side of the wafer, etc.) outside the region where the resist pattern is formed (hereinafter referred to as the pattern forming region). This method is effective when it is not necessary to irradiate the resist pattern region with ultraviolet rays. For example, when the resist pattern is formed according to Example 1 of the processing order, it is not necessary to irradiate the resist pattern region with ultraviolet rays.

[0305] In the above-described processing sequence example, development other than the development described above may be added. The additional development may be wet development or dry development.

[0306] Furthermore, when dry development is performed, the dry development may be performed repeatedly.

[0307] In addition, the metal-containing resist film can be formed by a CVD method or an ALD method. In this case, the metal-containing resist film can be formed outside the wafer processing apparatus 1, for example.

[0308] In each example of the above-mentioned treatment sequence, other treatment for vaporizing the solvent in the metal-containing resist film, such as natural drying or reduced-pressure drying, may be performed instead of the PAB treatment.

[0309] In addition, for a processing sequence in which PEB processing is performed multiple times, the first PEB processing may be performed outside the wafer processing apparatus 1. In addition, for a processing sequence in which PEB processing is performed only once, the PEB processing may also be performed outside the wafer processing apparatus 1.

[0310] The post-baking treatment can be omitted.

[0311] <Modification of Wafer Processing Apparatus 1>

[0312] The components of the wafer processing apparatus 1 can be omitted appropriately according to the processing sequence performed by the wafer processing apparatus 1. That is, when the wafer processing apparatus 1 performs only a part of the above-mentioned processing sequence, the components of the wafer processing apparatus 1 not used in the performed processing sequence can be omitted.

[0313] The embodiments of this specification are illustrative and non-limiting in all aspects. The above embodiments can be omitted, replaced or changed in various forms without departing from the main purpose of the present invention. For example, the constituent elements of the above embodiments can be arbitrarily combined. From this arbitrary combination, it is of course possible to obtain the effects and effects of each constituent element related to the combination, and it is possible to obtain other effects and effects that can be clearly understood by those skilled in the art from the description of this specification.

[0314] In addition, the effects described in this specification are only illustrative or exemplary and not restrictive. That is, the technology of the present invention can achieve other effects that can be clearly seen by those skilled in the art from the description of this specification in addition to or instead of the above effects.

[0315] In addition, the following structural examples also belong to the technical scope of the present invention.

[0316] (1) A substrate processing method, comprising:

[0317] A developing step is to develop the substrate on which a negative metal-containing resist film is formed and subjected to an exposure treatment and a heat treatment after the exposure treatment, using a polar developing material and a non-polar developing material.

[0318] (2) The substrate processing method as described in (1), wherein:

[0319] The developing process comprises:

[0320] Step a of developing using one of the polar developing material and the non-polar developing material, and

[0321] Then, a development step (b) is performed using the other of the polar developing material and the non-polar developing material.

[0322] (3) The substrate processing method as described in (2), wherein:

[0323] The one is the non-polar developing material, and the other is the polar developing material.

[0324] (4) The substrate processing method as described in (3), further comprising:

[0325] Step c, performing a heat treatment after the exposure treatment on the substrate on which the metal-containing resist film is formed and which has been subjected to the exposure treatment,

[0326] The step c includes a step of performing a heat treatment after the exposure treatment between the step a and the step b.

[0327] (5) The substrate processing method as described in (4), wherein:

[0328] The step c includes: performing a heating treatment after the exposure treatment before the step a.

[0329] (6) The substrate processing method as described in (2), wherein:

[0330] The one is the polar developing material, and the other is the non-polar developing material.

[0331] (7) The substrate processing method as described in (6), further comprising:

[0332] Step c, performing a heat treatment after the exposure treatment on the substrate on which the metal-containing resist film is formed and which has been subjected to the exposure treatment,

[0333] The c step comprises:

[0334] A step of performing a heating treatment after the first exposure treatment before the step a; and

[0335] A step of performing a second heat treatment after the exposure treatment between the step a and the step b.

[0336] (8) The substrate processing method as described in (1), wherein:

[0337] The developing process performs development using a mixture of the polar developing material and the non-polar developing material.

[0338] (9) The substrate processing method as described in any one of (1) to (4) and (6) to (8), further comprising:

[0339] A step of irradiating the entire surface of the substrate on which the metal-containing resist film is formed with ultraviolet rays before or after the exposure treatment of the substrate.

[0340] (10) The substrate processing method as described in (5), further comprising:

[0341] After the step of performing the heat treatment after the exposure treatment before the step a, the entire surface of the substrate is irradiated with ultraviolet rays before the step a.

[0342] (11) A substrate processing method as described in any one of (1) to (10), wherein:

[0343] The polar developing material is a solution of an alkaline material, water, a solution of an acidic material, or a vapor of any one of them.

[0344] (12) A substrate processing method as described in any one of (1) to (11), wherein:

[0345] The non-polar developing material is an organic solvent composed of molecules having an ester structure or an ether structure, a mixture of the organic solvent and an acidic material, or a vaporized product of any of them.

[0346] (13) A substrate processing method as described in any one of (1) to (12), wherein:

[0347] The metal contained in the metal-containing resist is tin.

[0348] (14) A substrate processing method as described in any one of (1) to (13), wherein:

[0349] The development step forms a pattern of the metal-containing resist having a pitch of 50 nm or less.

[0350] (15) A substrate processing method comprising:

[0351] An ultraviolet irradiation step of irradiating the entire surface of a substrate having a negative metal-containing resist film formed thereon with ultraviolet rays before or after the exposure treatment of the substrate; and

[0352] A developing step of developing the substrate having the coating formed thereon, subjected to the exposure treatment and the heat treatment after the exposure treatment, and subjected to the ultraviolet irradiation step, using a polar developing material.

[0353] (16) The substrate processing method as described in (15), wherein:

[0354] The invention further comprises: before the developing step, performing a heating process after the exposure process on the substrate on which the coating is formed and which has been subjected to the exposure process,

[0355] The ultraviolet irradiation step is performed after the step of performing the heat treatment after the exposure treatment.

[0356] (17) The substrate processing method as described in (15) or (16), wherein:

[0357] The polar developing material is a solution of an alkaline material, water, a solution of an acidic material, or a vapor of any one of them.

[0358] (18) A substrate processing method as described in any one of (15) to (17), wherein:

[0359] The metal contained in the metal-containing resist is tin.

[0360] (19) A substrate processing method as described in any one of (15) to (18), wherein:

[0361] The development step forms a pattern of the metal-containing resist having a pitch of 50 nm or less.

[0362] (20) A substrate processing device for processing a substrate, the substrate processing device comprising:

[0363] A developing section for developing the substrate using a polar developing material and a non-polar developing material; and

[0364] Control Department,

[0365] The control unit controls the substrate processing device to perform the following steps:

[0366] A step of developing the substrate on which a negative metal-containing resist film is formed and subjected to an exposure treatment and a heat treatment after the exposure treatment, using the polar developing material and the non-polar developing material.

[0367] (21) The substrate processing method as described in (6), further comprising:

[0368] Step c, performing a heat treatment after the exposure treatment on the substrate on which the metal-containing resist film is formed and the exposure treatment is performed,

[0369] The step c is performed only before the step a.

[0370] (22) The substrate processing method as described in any one of (15) to (19), further comprising:

[0371] A step of cleaning the peripheral portion of the substrate using a polar cleaning material during or following the developing step.

[0372] Description of Reference Numerals

[0373] 1 Wafer processing device

[0374] 5. Control Unit

[0375] 30 First development module

[0376] 31 Second development module

[0377] 32 Third development module

[0378] 120 Vacuum transfer chamber

[0379] 121 First dry developing module

[0380] 122 Second dry developing module

[0381] 123 Third dry developing module

[0382] W chip.

Claims

1. A substrate processing method, characterized in that: include: A developing step of developing a substrate on which a negative-type metal-containing resist film is formed and subjected to an exposure treatment and a heat treatment after the exposure treatment, using a polar developing material and a non-polar developing material.

2. The substrate processing method according to claim 1, wherein: The developing process comprises: a step of performing development using one of the polar developing material and the non-polar developing material; and Thereafter, a step (b) of developing is performed using the other of the polar developing material and the non-polar developing material.

3. The substrate processing method according to claim 2, characterized in that: The one is the non-polar developing material, and the other is the polar developing material.

4. The substrate processing method according to claim 3, characterized in that: Also includes: Step c, performing a heat treatment after the exposure treatment on the substrate on which the metal-containing resist film is formed and the exposure treatment is performed, The step c includes a step of performing a heat treatment after the exposure treatment between the step a and the step b.

5. The substrate processing method according to claim 4, characterized in that: The step c includes: performing a heating process after the exposure process before the step a.

6. The substrate processing method according to claim 2, wherein: The one is the polar developing material, and the other is the non-polar developing material.

7. The substrate processing method according to claim 6, characterized in that: Also includes: Step c, performing a heat treatment after the exposure treatment on the substrate on which the metal-containing resist film is formed and the exposure treatment is performed, The c step comprises: A step of performing a heating treatment after the first exposure treatment before the step a; and A step of performing a second heat treatment after the exposure treatment between the step a and the step b.

8. The substrate processing method according to claim 1, wherein: The developing process performs development using a mixture of the polar developing material and the non-polar developing material.

9. The substrate processing method according to any one of claims 1 to 4 and 6 to 8, characterized in that: Also includes: A step of irradiating the entire surface of the substrate on which the coating film containing the metal resist is formed with ultraviolet rays before or after the exposure treatment of the substrate.

10. The substrate processing method according to claim 5, characterized in that: Also includes: After the step of performing the heat treatment after the exposure treatment before the step a, a step of irradiating the entire surface of the substrate with ultraviolet rays before the step a is performed.

11. The substrate processing method according to any one of claims 1 to 8 and 10, characterized in that: The polar developing material is a solution of an alkaline material, water, a solution of an acidic material, or a vapor of any one of them.

12. The substrate processing method according to any one of claims 1 to 8 and 10, characterized in that: The non-polar developing material is an organic solvent composed of molecules having an ester structure or an ether structure, a mixture of the organic solvent and an acidic material, or a vaporized product of any of them.

13. The substrate processing method according to any one of claims 1 to 8 and 10, characterized in that: The metal contained in the metal-containing resist is tin.

14. The substrate processing method according to any one of claims 1 to 8 and 10, characterized in that: The development step forms a pattern of the metal-containing resist having a pitch of 50 nm or less.

15. A substrate processing method, characterized in that: include: An ultraviolet irradiation step of irradiating the entire surface of a substrate on which a negative-type metal resist-containing coating is formed with ultraviolet rays before or after the exposure treatment of the substrate; and A developing step of developing the substrate on which the coating film is formed, the exposure treatment and the heat treatment after the exposure treatment are performed, and the ultraviolet irradiation step is performed using a polar developing material.

16. The substrate processing method according to claim 15, characterized in that: Also includes: Before the developing step, a step of performing a post-exposure heating treatment on the substrate having the coating formed thereon and subjected to the exposure treatment, The ultraviolet irradiation step is performed after the step of performing the heat treatment after the exposure treatment.

17. The substrate processing method according to claim 15 or 16, characterized in that: The polar developing material is a solution of an alkaline material, water, a solution of an acidic material, or a vapor of any one of them.

18. The substrate processing method according to claim 15 or 16, characterized in that: The metal contained in the metal-containing resist is tin.

19. The substrate processing method according to claim 15 or 16, characterized in that: Also includes: A step of cleaning the peripheral portion of the substrate using a polar cleaning material during or following the developing step.

20. A substrate processing device for processing a substrate, wherein the substrate processing device comprises: A developing section for developing the substrate using a polar developing material and a non-polar developing material; and Control Department, The control unit controls the substrate processing device to perform the following steps: A step of developing a substrate on which a negative-type metal-containing resist film is formed and which has been subjected to an exposure treatment and a heat treatment after the exposure treatment, using the polar developing material and the non-polar developing material.

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