WO2023238737A1 - 基板処理方法、記憶媒体、及び基板処理装置 - Google Patents

基板処理方法、記憶媒体、及び基板処理装置 Download PDF

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Publication number
WO2023238737A1
WO2023238737A1 PCT/JP2023/020108 JP2023020108W WO2023238737A1 WO 2023238737 A1 WO2023238737 A1 WO 2023238737A1 JP 2023020108 W JP2023020108 W JP 2023020108W WO 2023238737 A1 WO2023238737 A1 WO 2023238737A1
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WIPO (PCT)
Prior art keywords
water
substrate
resist
substrate processing
soluble material
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PCT/JP2023/020108
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English (en)
French (fr)
Japanese (ja)
Inventor
剛 下青木
アルノ アライン ジャン ダウエンドルファー
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東京エレクトロン株式会社
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Publication of WO2023238737A1 publication Critical patent/WO2023238737A1/ja

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34

Definitions

  • the present disclosure relates to a substrate processing method, a storage medium, and a substrate processing apparatus.
  • Patent Document 1 discloses a method for forming a fine resist pattern, in which a resist pattern with a thick line width is formed, and then the entire surface is exposed and developed to reduce the line width.
  • the present disclosure provides a technique effective for suppressing defects in resist patterns.
  • a substrate processing method includes forming a concavo-convex pattern using a resist on a substrate, including a development process, and reinforcing convex portions by supplying a water-soluble material liquid to concave portions of the concave-convex pattern. performing a hardening treatment on the convex portion; and removing a portion of the concavo-convex pattern including the portion reinforced in the reinforcing.
  • FIG. 1 is a schematic diagram illustrating a schematic configuration of a substrate processing system.
  • FIG. 2 is a schematic diagram illustrating the internal configuration of the coating and developing device.
  • FIG. 3 is a schematic diagram illustrating the configuration of the developing unit.
  • FIG. 4 is a schematic diagram illustrating the configuration of the heat treatment unit.
  • FIG. 5 is a block diagram illustrating the hardware configuration of the control device.
  • FIG. 6 is a flowchart showing an example of the development processing procedure.
  • 7(a) to 7(d) are schematic diagrams illustrating an example of the procedure shown in FIG. 6.
  • FIG. 8 is a flowchart illustrating an example of a modification of the first stage of the development processing procedure from the formation of a processed film.
  • 9(a) to 9(d) are schematic diagrams illustrating an example of the procedure shown in FIG. 8.
  • the substrate processing system 1 is a system that forms a photosensitive film on a substrate, exposes the photosensitive film, and develops the photosensitive film.
  • the work W to be processed is, for example, a substrate, or a substrate on which a film, a circuit, or the like is formed by performing a predetermined process.
  • the substrate included in the workpiece W is, for example, a wafer containing silicon.
  • the workpiece W (substrate) may be formed in a circular shape.
  • the workpiece W to be processed may be a glass substrate, a mask substrate, an FPD (Flat Panel Display), or the like, or may be an intermediate obtained by performing predetermined processing on these substrates.
  • the photosensitive film is, for example, a resist film.
  • the substrate processing system 1 includes a coating/developing device 2, an exposure device 3, and a control device 100.
  • the exposure device 3 is a device that exposes a resist film (photosensitive film) formed on a workpiece W (substrate). Specifically, the exposure device 3 irradiates the exposure target portion of the resist film with energy rays for exposure using a method such as immersion exposure.
  • the coating/developing device 2 performs a process of coating a resist (chemical solution) on the surface of the workpiece W (substrate) to form a resist film before the exposure process by the exposure device 3 . Further, the coating/developing device 2 performs a developing process on the resist film after the exposure process.
  • the coating/developing device 2 (Substrate processing equipment) The configuration of the coating/developing device 2 will be described below as an example of a substrate processing device. As shown in FIGS. 1 and 2, the coating/developing device 2 (substrate processing device) includes a carrier block 4, a processing block 5, and an interface block 6.
  • the carrier block 4 introduces the workpiece W into the coating/developing device 2 and extracts the workpiece W from the coating/developing device 2 .
  • the carrier block 4 can support a plurality of carriers C for workpieces W, and has a built-in transport device A1 including a delivery arm.
  • the carrier C accommodates a plurality of circular workpieces W, for example.
  • the transport device A1 takes out the workpiece W from the carrier C, passes it to the processing block 5, receives the workpiece W from the processing block 5, and returns it into the carrier C.
  • the processing block 5 has a plurality of processing modules 11, 12, 13, and 14.
  • the processing module 11 includes a coating unit U1, a heat treatment unit U2, and a transport device A3 that transports the workpiece W to these units.
  • the processing module 11 forms a lower layer film on the surface of the workpiece W using a coating unit U1 and a heat treatment unit U2.
  • the coating unit U1 coats the workpiece W with a processing liquid for forming a lower layer film.
  • the heat treatment unit U2 performs various heat treatments associated with the formation of the lower layer film.
  • the processing module 12 includes a coating unit U1, a heat treatment unit U2, and a transport device A3 that transports the workpiece W to these units.
  • the processing module 12 forms a resist film on the lower layer film using a coating unit U1 and a heat treatment unit U2.
  • the coating unit U1 coats a resist onto the lower layer film as a processing liquid for resist film formation.
  • the heat treatment unit U2 performs various heat treatments associated with the formation of a resist film. As a result, a resist film is formed on the surface of the workpiece W.
  • the processing module 13 includes a coating unit U1, a heat treatment unit U2, and a transport device A3 that transports the workpiece W to these units.
  • the processing module 13 forms an upper layer film on the resist film using the coating unit U1 and the heat treatment unit U2.
  • the coating unit U1 applies a processing liquid for forming an upper layer film onto the resist film.
  • the heat treatment unit U2 performs various heat treatments associated with the formation of the upper layer film.
  • the processing module 14 includes a development unit U3 (development processing section, reinforcement processing section, removal processing section), a heat processing unit U4 (reinforcement processing section, hardening processing section), and a transport device A3 that transports the workpiece W to these units. Built-in.
  • the processing module 14 uses a developing unit U3 and a heat processing unit U4 to perform a series of processes including a developing process for the resist film after exposure.
  • the developing unit U3 partially removes the resist film (performs a developing process) by applying (supplying) a developer onto the surface of the exposed workpiece W. In other words, the developing unit U3 forms a resist pattern that is a concavo-convex pattern on the surface of the workpiece W.
  • the developing unit U3 supplies a rinsing liquid to the surface of the workpiece W in order to wash away the developing liquid. Furthermore, after replacing the rinsing liquid in the recesses of the resist pattern with the processing liquid, the developing unit U3 forms a reinforcing material in the recesses (see FIG. 9(b)).
  • the heat treatment unit U4 performs various heat treatments associated with development processing. Specific examples of the heat treatment accompanying the development treatment include heat treatment before the development treatment (PEB: Post Exposure Bake), heat treatment after the development treatment (PB: Post Bake), and the like.
  • a shelf unit U10 is provided on the carrier block 4 side within the processing block 5.
  • the shelf unit U10 is divided into a plurality of cells arranged in the vertical direction.
  • a transport device A7 including a lifting arm is provided near the shelf unit U10. The transport device A7 moves the work W up and down between the cells of the shelf unit U10.
  • a shelf unit U11 is provided on the interface block 6 side within the processing block 5.
  • the shelf unit U11 is divided into a plurality of cells arranged in the vertical direction.
  • the interface block 6 transfers the workpiece W to and from the exposure apparatus 3.
  • the interface block 6 has a built-in transport device A8 including a delivery arm, and is connected to the exposure device 3.
  • the transport device A8 transfers the work W placed on the shelf unit U11 to the exposure device 3.
  • the transport device A8 receives the workpiece W from the exposure device 3 and returns it to the shelf unit U11.
  • the developing unit U3 includes a rotation holding section 20 and three liquid supply sections 30a, 30b, and 30c.
  • the development unit U3 can function as a development processing section, a reinforcement processing section, and a removal processing section in the exposure/development device 2.
  • the rotation holding section 20 includes a rotation driving section 21, a shaft 22, and a holding section 23.
  • the rotation drive unit 21 operates based on an operation signal from the control device 100 and rotates the shaft 22.
  • the rotation drive unit 21 includes, for example, an electric motor or the like as a power source.
  • the holding part 23 is provided at the tip of the shaft 22.
  • a workpiece W is placed on the holding portion 23 .
  • the holding unit 23 holds the workpiece W substantially horizontally, for example, by suction or the like. That is, the rotation holding unit 20 rotates the workpiece W around a central axis (rotation axis) perpendicular to the surface Wa of the workpiece W while the posture of the workpiece W is substantially horizontal. In the example of FIG. 3, the rotation holding section 20 rotates the workpiece W at a predetermined number of rotations counterclockwise when viewed from above.
  • the liquid supply unit 30a supplies the developer L1 to the surface Wa of the workpiece W.
  • the developer L1 is a chemical solution for performing a development process on the resist film R to form a resist pattern.
  • a portion of the resist film R that is irradiated with the exposure energy beam reacts and is removed. . That is, a positive resist pattern (resist material) may be used.
  • An example of the developer L1 for removing the exposed area is an alkaline solvent.
  • a negative resist pattern resist material
  • An example of the developer L1 for removing the unexposed area is an organic solvent.
  • the liquid supply unit 30b supplies the rinsing liquid L2 to the surface Wa of the workpiece W (the resist film R on which the resist pattern is formed).
  • the rinsing liquid L2 may be any chemical liquid that can wash away the developing liquid L1.
  • the rinse liquid L2 may be water (pure water).
  • the liquid supply section 30a and the liquid supply section 30b constitute a development processing section that performs development processing on the resist film R.
  • the liquid supply section 30c (reinforcement processing section) supplies the processing liquid L3 to the surface Wa of the workpiece W.
  • the processing liquid L3 is a chemical liquid for forming a water-soluble material as a reinforcing material in the recesses of the resist pattern.
  • the treatment liquid L3 may be a chemical liquid that can be supplied to the workpiece W in a liquid state and that dries and solidifies by a predetermined process (for example, rotation of the workpiece W).
  • the treatment liquid L3 may be, for example, a water-soluble material liquid containing a water-soluble adsorbent polymer.
  • the water-soluble material liquid refers to a liquid in which a water-soluble material is dissolved in a liquid using water as a solvent.
  • the water-soluble adsorbent polymer may be a polymer that has adsorption properties to the resist pattern, and may be, for example, a vinyl acetate emulsion or an acrylic emulsion.
  • the processing liquid L3 contains a specific component, the content may be adjusted depending on the characteristics of the resist film R, etc. to which the processing liquid L3 is supplied.
  • the liquid supply units 30a, 30b, and 30c each include a liquid source 31, a valve 33, a nozzle 34, and a pipe 35.
  • the liquid sources 31 of the liquid supply units 30a, 30b, and 30c supply chemical liquids to the nozzles 34 via valves 33 and piping 35, respectively.
  • the nozzles 34 of the liquid supply units 30a, 30b, and 30c are each arranged above the work W so that the discharge ports face the surface Wa of the work W.
  • the nozzle 34 discharges the chemical liquid supplied from the liquid source 31 toward the surface Wa of the workpiece W.
  • Piping 35 connects between liquid source 31 and nozzle 34 .
  • the valve 33 switches the flow path within the pipe 35 between an open state and a closed state.
  • the developing unit U3 may include a drive mechanism (not shown) that reciprocates the nozzle 34 in the horizontal direction.
  • the heat treatment unit U4 includes a hot plate 44, a chamber 40, a plurality of support pins 46, and a gas supply section 50.
  • the heat treatment unit U4 functions as a reinforcement processing section and a hardening processing section in the exposure/development device 2.
  • the hot plate 44 includes a heater 45.
  • the hot plate 44 supports a workpiece W to be heat treated (a target for solvent removal) and heats the supported workpiece W.
  • the hot plate 44 is formed into a substantially disk shape, for example.
  • the diameter of the hot plate 44 may be larger than the diameter of the workpiece W.
  • the hot plate 44 may be made of a metal with high thermal conductivity, such as aluminum, silver, or copper.
  • the heater 45 increases the temperature of the hot plate 44.
  • the heater 45 may be composed of a resistance heating element. When a current flows through the heater 45 according to an instruction from the control device 100, the heater 45 generates heat. Then, the heat from the heater 45 is transferred, and the temperature of the hot plate 44 rises.
  • the chamber 40 forms a heat treatment space in which heat treatment is performed.
  • the chamber 40 includes an upper chamber 41 and a lower chamber 42.
  • the upper chamber 41 is connected to a drive unit (not shown) and moves vertically relative to the lower chamber 42.
  • the upper chamber 41 includes a top plate facing the work W on the hot plate 44 and a side wall surrounding the work W on the hot plate 44 .
  • the lower chamber 42 includes a holding portion 43 and holds a hot plate 44 .
  • the support pin 46 is a pin that supports the workpiece W from below.
  • the support pin 46 extends in the vertical direction so as to pass through the hot plate 44.
  • the plurality of support pins 46 may be arranged at equal intervals in the circumferential direction around the center of the hot plate 44 .
  • the drive unit 47 raises and lowers the support pin 46 according to instructions from the control device 100.
  • the drive unit 47 is, for example, a lifting actuator.
  • the gas supply unit 50 is configured to supply gas into the chamber 40 (heat treatment space).
  • the gas supply unit 50 supplies nitrogen gas into the chamber 40 .
  • the gas supply section 50 includes a gas supply source 53, a valve 52, and a pipe 54.
  • the gas supply source 53 functions as a gas supply source.
  • the valve 52 switches between an open state and a closed state according to instructions from the control device 100.
  • the gas supply source 53 sends gas into the chamber 40 (heat treatment space) via the pipe 54 when the valve 52 is in the open state.
  • Control device 100 partially or entirely controls substrate processing system 1 .
  • the control device 100 forms an uneven pattern using a resist on the surface Wa of the workpiece W, performs a process of forming a reinforcing portion on the uneven pattern, and performs a hardening process of the reinforced uneven pattern.
  • the present invention is configured to remove a portion of the uneven pattern including the reinforcing portion.
  • the control device 100 is composed of one or more control computers.
  • the control device 100 has a circuit 120 shown in FIG. Circuit 120 includes one or more processors 121, memory 122, storage 123, and input/output ports 124.
  • the storage 123 includes a computer-readable storage medium such as a hard disk.
  • the storage medium stores a program for causing the control device 100 to execute a substrate processing procedure described below.
  • the storage medium may be a removable medium such as a nonvolatile semiconductor memory, a magnetic disk, or an optical disk.
  • the memory 122 temporarily stores programs loaded from the storage medium of the storage 123 and the results of calculations performed by the processor 121 .
  • the processor 121 cooperates with the memory 122 to execute the above program, thereby configuring a plurality of functional modules for executing the substrate processing procedure described below.
  • the input/output port 124 inputs and outputs electrical signals to and from a member to be controlled according to instructions from the processor 121.
  • each of the plurality of functional modules may be realized by an individual control computer.
  • each of these functional modules may be realized by a combination of two or more control computers.
  • the plurality of control computers may be communicably connected to each other and may cooperate to execute the substrate processing procedure described below.
  • the hardware configuration of the control device 100 is not necessarily limited to one in which each functional module is configured by a program.
  • each functional module of the control device 100 may be constituted by a dedicated logic circuit or an ASIC (Application Specific Integrated Circuit) that integrates the logic circuit.
  • ASIC Application Specific Integrated Circuit
  • the control device 100 controls the substrate processing system 1 to perform substrate processing including coating and developing processing, for example, in the following steps. First, the control device 100 controls the transport device A1 to transport the work W in the carrier C to the shelf unit U10, and controls the transport device A7 to place the work W in the cell for the processing module 11.
  • control device 100 controls the transport device A3 to transport the work W on the shelf unit U10 to the coating unit U1 and heat treatment unit U2 in the processing module 11. Further, the control device 100 controls the coating unit U1 and the heat treatment unit U2 so as to form a lower layer film on the surface Wa of the workpiece W. Thereafter, the control device 100 controls the transport device A3 to return the work W on which the lower layer film has been formed to the shelf unit U10, and controls the transport device A7 to place the work W in the cell for the processing module 12. .
  • control device 100 controls the transport device A3 to transport the work W on the shelf unit U10 to the coating unit U1 and heat treatment unit U2 in the processing module 12. Further, the control device 100 controls the coating unit U1 and the heat treatment unit U2 to form the resist film R on the lower layer film of the workpiece W. Thereafter, the control device 100 controls the transport device A3 to return the work W to the shelf unit U10, and controls the transport device A7 to place the work W in the cell for the processing module 13.
  • control device 100 controls the transport device A3 to transport the work W on the shelf unit U10 to each unit in the processing module 13. Further, the control device 100 controls the coating unit U1 and the heat treatment unit U2 so as to form an upper layer film on the resist film R of the workpiece W. After that, the control device 100 controls the transport device A3 to transport the workpiece W to the shelf unit U11.
  • control device 100 controls the transport device A8 to send the work W stored in the shelf unit U11 to the exposure device 3. Then, in the exposure device 3, the resist film R formed on the workpiece W is exposed to light. Thereafter, the control device 100 controls the transport device A8 to receive the exposed workpiece W from the exposure device 3 and to place the workpiece W in the cell for the processing module 14 in the shelf unit U11.
  • control device 100 controls the transport device A3 to transport the work W on the shelf unit U11 to the heat treatment unit U4 of the processing module 14. Then, the control device 100 performs control to execute a series of processing procedures (hereinafter referred to as "development processing procedures") including heat treatment accompanying the development processing and development processing. Details of this development processing procedure will be described later. A resist pattern is formed on the front surface Wa of the workpiece W by executing the development processing procedure. With the above steps, the substrate processing including coating and developing processing is completed.
  • FIG. 6 is a flowchart showing an example of the development processing procedure.
  • the control device 100 executes step S01.
  • the control device 100 controls the coating unit U1 and the exposure device 3 to form a treatment film and perform exposure processing on the workpiece W.
  • the control device 100 controls the transport device A3 to transport the work W after exposure by the exposure device 3 to the heat treatment unit U4.
  • step S02 the control device 100 controls the heat treatment unit U4 to perform heat treatment on the exposed workpiece W at a predetermined temperature for a predetermined time. Then, the control device 100 controls the transport device A3 to transport the workpiece W, which has been subjected to the heat treatment before development, to the development unit U3.
  • step S03 as a first development process, the control device 100 controls the development unit U3 to supply the developer L1 to the resist film R formed on the surface Wa of the workpiece W.
  • the control device 100 discharges the developer L1 from the nozzle 34 by opening the valve 33 of the liquid supply section 30a while controlling the rotation drive section 21 so that the workpiece W rotates at a predetermined rotation speed.
  • the resist film R is developed, and a resist pattern 200A having a plurality of convex portions 201 and a plurality of concave portions 202 is formed on the surface Wa of the workpiece W (see FIG. 7(a)).
  • the convex portion 201 is basically an area where no exposure is performed, but the surface of the convex portion 201, that is, the vicinity of the surface of the surface corresponding to the concave portion 202 becomes an intermediate exposure region 201a where exposure partially progresses. .
  • step S03 is a first development process, and is not a stage of forming a completed resist pattern. Therefore, in the resist pattern 200A formed after step S03, the width of the convex portion 201 is larger than that of the resist pattern finally formed on the workpiece W. In other words, because the intermediate exposure region 201a remains, the convex portion 201 is larger than the desired pattern shape. On the other hand, the recess 202 is smaller than the resist pattern that will eventually be formed on the workpiece W. In the resist pattern 200A, the lower width of the convex portion 201 may be larger than the upper width, which is a so-called footing shape. At this time, the side surface of the convex portion 201 may be inclined so that the width is wider at the bottom. Steps S01 to S03 up to this point correspond to forming an uneven pattern using resist.
  • step S04 the control device 100 controls the developing unit U3 to supply the processing liquid L3, that is, the water-soluble material liquid, to the workpiece W.
  • the control device 100 causes the developing unit U3 to start supplying the processing liquid L3 to the surface Wa of the workpiece W.
  • the control device 100 controls the rotation drive unit 21 so that the workpiece W rotates at a predetermined rotation speed, and opens the valve 33 of the liquid supply unit 30c to supply the processing liquid L3 from the nozzle 34.
  • the developing unit U3 is caused to start discharging.
  • the control device 100 causes the developing unit U3 to continue rotating the workpiece W and supplying the processing liquid L3 to the surface Wa of the workpiece W for a predetermined period of time.
  • the processing liquid L3 is introduced into the recess 202 on the surface Wa (see FIG. 7(b)).
  • the supply amount of the processing liquid L3 can be adjusted to such an extent that the recess 202 is not filled with the processing liquid L3. That is, the upper surface of the convex portion 201 can be adjusted to be above the water surface of the processing liquid L3.
  • the control device 100 controls the transport device A3 to transport the workpiece W supplied with the processing liquid L3 (water-soluble material liquid) to the heat treatment unit U4.
  • Step S04 corresponds to reinforcing the convex portion by supplying a water-soluble material liquid.
  • step S05 the control device 100 controls the heat treatment unit U4 to perform heat treatment on the exposed workpiece W at a predetermined temperature for a predetermined time.
  • the control device 100 controls the heat treatment unit U4 to perform heat treatment on the exposed workpiece W at a predetermined temperature for a predetermined time.
  • the water-soluble material liquid staying in the recess 202 of the workpiece W is heated, thereby solidifying the water-soluble material inside. do.
  • a water-soluble material adheres as a water-soluble film M to the surface of the convex portion 201 that contacts the processing liquid L3 within the concave portion 202.
  • Step S05 corresponds to reinforcing the convex portion by supplying a water-soluble material liquid, and also corresponds to performing a hardening process on the convex portion.
  • the adsorbent polymer is hardened. By covering a portion of the surface of the convex portion 201, deformation of the convex portion 201 can be prevented.
  • the heating temperature in step S05 is set to a temperature lower than the glass transition temperature Tg of the adsorptive polymer.
  • the adsorbent polymer dries and solidifies, forming a water-soluble film M covering a part of the intermediate exposure region 201a. Note that the water-soluble film M can be formed even when the heating temperature is set to be higher than the glass transition temperature Tg and the difference therebetween does not become large.
  • step S05 By performing the heating in step S05 with the film reinforced by the water-soluble film M, the strength of the resist itself forming the convex portions 201 is improved, so that pattern collapse is suppressed.
  • step S05 when the formation of the water-soluble film M is promoted on the side closer to the lower side of the convex portion 201 (the surface Wa of the workpiece W), the reinforcing hardening of the convex portion 201 by the adsorbent polymer is also enhanced. Therefore, in step S05, the conditions of each part of the heat treatment unit U4 may be changed so that the concentration of the treatment liquid L3 (water-soluble material liquid) is lower on the upper side and higher on the lower side. Specifically, by increasing the humidity above the workpiece W in the heat treatment unit U4 or spraying pure water above the workpiece W, the lower side of the convex portion 201 (the surface Wa of the workpiece W) is heated. It is conceivable to relatively increase the concentration of the processing liquid L3 on the near side.
  • control device 100 controls the transport device A3 to transport the workpiece W to the developing unit U3.
  • step S06 as a second development process, the control device 100 controls the development unit U3 to supply a developer based on the rinse liquid L2 to the resist film R formed on the surface Wa of the workpiece W.
  • the control device 100 discharges the rinsing liquid L2 from the nozzle 34 by opening the valve 33 of the liquid supply section 30b while controlling the rotation drive section 21 so that the workpiece W rotates at a predetermined rotation speed. let As a result, the resist pattern 200A is developed.
  • Step S06 corresponds to removing a part of the uneven pattern including the reinforced part in the reinforcement.
  • the second development process in step S06 is aimed at removing the water-soluble film M. Therefore, similarly to the first development process, the development process using the developer L1 is not performed, and the development conditions are adjusted so that the amount of resist material removed is reduced. Therefore, the process is performed using, for example, the rinse liquid L2.
  • the water-soluble film M is heated and hardened in step S05, it may be difficult to remove the water-soluble film M with pure water.
  • a configuration may be adopted in which a liquid in which a small amount of the developer L1 is mixed with the rinse liquid L2 is prepared and supplied to the workpiece W.
  • the treatment may be performed using a heated liquid of the rinsing liquid L2.
  • a liquid obtained by mixing the rinsing liquid L2 and an activator may be prepared separately, and the treatment may be performed using this liquid.
  • step S06 not only the water-soluble film M but also a part of the resist pattern around it is removed.
  • the intermediate exposure region 201a existing around the water-soluble film M can be removed even if it is not covered with the water-soluble film M at this stage.
  • a resist pattern 200B having a plurality of convex portions 203 and a plurality of concave portions 204 is formed on the surface Wa of the workpiece W, as shown in FIG. 7(d).
  • This resist pattern 200B has a pattern size suitable for subsequent processing. That is, the convex portions 203 and the concave portions 204 correspond to the shape of the resist pattern that is finally required.
  • the size of the resist pattern 200B can also be adjusted by adjusting the processing conditions in the second development process in step S06.
  • the treatment liquid L3 may be a water-soluble material liquid in which a fluororesin is mixed with an aqueous solvent. Furthermore, the aqueous liquid containing the fluororesin may contain carboxylic acid.
  • the fluororesin when the water-soluble material is a fluororesin, the fluororesin turns into a rubber state and covers part of the surface of the protrusion 201, thereby preventing the protrusion 201 from being deformed.
  • the heating temperature in step S05 described above is set to be higher than the glass transition temperature Tg of the fluororesin.
  • the fluororesin becomes a rubber state, and a denser film is formed as the water-soluble film M covering a part of the intermediate exposure region 201a.
  • the flexibility (elasticity) of this dense film can be used to prevent the convex portion 201 from falling down.
  • the water-soluble film M contains the carboxylic acid component.
  • the scum removal performance is improved in the second development process in step S06.
  • the carboxylic acid facilitates the removal of the water-soluble membrane M and the surrounding scum.
  • the treatment liquid L3 may be a water-soluble material liquid containing a crosslinking agent.
  • the crosslinking agent is a component that promotes curing due to crosslinking in the resist film.
  • the crosslinking agent enters the intermediate exposure region 201a of the convex portion 201, so that while the water-soluble film M is formed on the surface, the intermediate exposure region inside thereof is Crosslinking of the resist material at 201a progresses.
  • the intermediate exposure region 201a is further hardened, so that deformation of the convex portion 201 can be prevented.
  • the heating temperature in step S05 may be set to a temperature lower than the glass transition temperature Tg of the crosslinking agent.
  • the water-soluble film M can be formed even when the heating temperature is set to be higher than the glass transition temperature Tg and the difference therebetween does not become large.
  • the water-soluble film M may be uneven due to the non-uniform distribution of the contained components within the resist film, or more specifically, due to the action of the acid from the resist.
  • the pattern may become uniform, and as a result, the shape of the pattern may be affected. Therefore, when performing the above processing on a resist material suitable for EUV exposure, it is conceivable to use an adsorbent polymer-containing water-soluble material liquid as the processing liquid L3, which is not affected by the action of acids.
  • step S02 (About automatic control of development processing procedures)
  • the conditions for the two heating processes individually it is necessary to not only look at the conditions for the two heating processes individually, but also to It is necessary to adjust the total amount depending on the material.
  • the amount of heat applied to the resist material is determined depending on the type of resist material, the shape of the final resist pattern, etc.
  • the conditions (temperature, time, etc.) for the heat treatment before development (step S02) can be set depending on the type of resist material amount, the film quality (degree of hardening) of the pattern required after the heat treatment, and the like.
  • the conditions of the heat treatment before development (step S02) can be changed depending on the state of the resist pattern after heat treatment and the state of the resist pattern after development processing.
  • the conditions for the heat treatment before development (step S02) may be changed depending on various circumstances. Therefore, the heat treatment of the water-soluble material liquid (step S05) needs to be determined in consideration of the amount of heat that should be applied to the resist material.
  • the heating conditions in the heat treatment of the water-soluble material liquid (step S05) are determined by taking into account the conditions of the heat treatment before development (step S02), and the temperature history of the resist material is determined to form the resist pattern that is ultimately desired. should be adjusted to provide appropriate conditions.
  • the control device 100 automatically adjusts the heating conditions of the heat treatment of the water-soluble material liquid (step S05). Adjustment control may also be performed.
  • the control device 100 may be configured to correct the heat treatment of the water-soluble material liquid (step S05) according to the processing conditions of the heat treatment before development (step S02).
  • step S02 For example, if the conditions of the heat treatment before development (step S02) are such that the amount of heat is less than a predetermined reference value, the amount of heat given to the resist material in the heat treatment of the water-soluble material solution (step S05) is increased. You may change the conditions as follows. With such a configuration, a change in the amount of heat in the first stage heat treatment can be adjusted in the second stage heat treatment.
  • step S11 the control device 100 controls the coating unit U1 to form the first treatment film 205 on the work W.
  • the first treatment film 205 is a thin film formed on the surface Wa of the workpiece W, and is formed to cover the entire surface Wa.
  • step S12 the control device 100 performs a process of curing the first treated film 205 of the workpiece W.
  • the first treated film 205 formed on the surface Wa of the workpiece W is irradiated with UV light (ultraviolet light), thereby curing the first treated film 205 .
  • the first treated film 205 is entirely irradiated with UV light.
  • the control device 100 may control the transport device A3 to transport the workpiece W to a unit capable of irradiating UV light, for example.
  • step S13 the control device 100 controls the coating unit U1 to form the second treatment film 206 on the first treatment film 205 of the workpiece W.
  • the second treated film 206 is a film formed entirely on the first treated film 205 of the workpiece W.
  • the film thickness at the time of coating is adjusted so that the total thickness of the first treated film 205 and the second treated film 206 is equivalent to the resist pattern 200A.
  • step S14 the control device 100 transports the workpiece W to the exposure device 3 and then controls the exposure device 3 so as to perform exposure processing on the workpiece W.
  • regions of the first treated film 205 and the second treated film 206 that will become recesses in the resist pattern are exposed. That is, as shown in FIG. 9(b), the first treated film 205b at the position corresponding to the recess in the first treated film 205, and the second treatment at the position corresponding to the recess in the second treated film 206.
  • the film 206b is the exposed treated film.
  • the second treated film 206a formed at the position corresponding to the convex portion of the second treated film 206 and the first treated film 205 located below the second treated film 206a are not exposed.
  • step S15 the control device 100 controls the heat treatment unit U4 to perform heat treatment on the exposed workpiece W at a predetermined temperature for a predetermined time. Then, the control device 100 controls the transport device A3 to transport the workpiece W, which has been subjected to the heat treatment before development, to the development unit U3.
  • the difference in reactivity to the developer between the exposed and unexposed parts of the first treated film 205 and the second treated film 206 becomes clear, making it easier to form a pattern.
  • step S16 as a first development process, the control device 100 controls the development unit U3 to supply the developer L1 to the first treatment film 205 and the second treatment film 206 formed on the surface Wa of the workpiece W. do.
  • the control device 100 discharges the developer L1 from the nozzle 34 by opening the valve 33 of the liquid supply section 30a while controlling the rotation drive section 21 so that the workpiece W rotates at a predetermined rotation speed.
  • the resist film is developed, and a resist pattern 200C having a plurality of convex portions 207 and a plurality of concave portions 208 is formed on the surface Wa of the workpiece W (see FIG. 9(c)).
  • the portion of the resist film that is not removed becomes the convex portion 207
  • the portion of the resist film that is removed becomes the convex portion 207.
  • the convex portion 207 is basically an unexposed region when the resist is a positive type resist, but the surface of the convex portion 207, that is, the vicinity of the surface of the surface corresponding to the concave portion 208 is Similar to the intermediate exposure area 201a shown in ), this is an intermediate exposure area where exposure partially progresses.
  • the convex portions of the pattern are generally the exposed portions, and near the surface, intermediate exposed regions where the degree of exposure is small are formed.
  • the lower part of the convex portion 207 is formed by the first treated film 205 below the second treated film 206a, as described above.
  • This portion may have a so-called footing shape in which the width thereof is larger than the upper portion, similar to the lower portion of the convex portion 201 described above.
  • the control device 100 controls the developing unit U3 to supply the processing liquid L3, that is, the water-soluble material liquid, to the workpiece W. Specifically, the control device 100 causes the developing unit U3 to start supplying the processing liquid L3 to the plurality of recesses 208 formed on the surface Wa of the workpiece W. For example, the control device 100 controls the rotation drive unit 21 so that the workpiece W rotates at a predetermined rotation speed, and opens the valve 33 of the liquid supply unit 30c to supply the processing liquid L3 from the nozzle 34. The developing unit U3 is caused to start discharging.
  • Step S16 corresponds to reinforcing the convex portion by supplying a water-soluble material liquid.
  • the water-soluble material liquid is supplied before the developer L1 supplied to the surface Wa of the workpiece W in the first development process is dried, that is, before the surface Wa of the workpiece W is dry. It's okay to be hurt.
  • step S17 the control device 100 performs a process of curing the resist pattern 200C on the developed workpiece W.
  • the resist pattern 200C formed on the surface Wa of the workpiece W is irradiated with UV light (ultraviolet light) to harden the resist pattern 200C.
  • UV light ultraviolet light
  • FIG. 9(d) the entire surface of the resist pattern 200C is irradiated with UV light.
  • the control device 100 may control the transport device A3 to transport the workpiece W to a unit capable of irradiating UV light, for example.
  • step S06 the second development process shown in FIG. 6 is performed.
  • curing of the resist pattern 200C is promoted even before the water-soluble material liquid is supplied, so it is expected that pattern collapse can be further suppressed.
  • the timing of supplying the water-soluble material liquid may be changed.
  • a water-soluble material solution is applied at the first development processing stage (step S16).
  • the feeding procedure may be changed.
  • the water-soluble material liquid may be supplied to the surface Wa of the workpiece W after the curing process (step S17).
  • the second development process (step S06) may be performed after the heat treatment (step S05) shown in FIG. 6 is performed. In this way, the supply timing of the water-soluble material liquid may be adjusted, and the previous and subsequent processes may be changed depending on the supply timing.
  • the curing process is performed with the convex portions 201 of the resist pattern 200A reinforced by supplying the water-soluble material liquid as the treatment liquid L3. This prevents the pattern of the portion 201 from collapsing. Further, since the reinforced portion is removed after the hardening process of the convex portion 201, problems caused by remaining water-soluble material are also prevented. Therefore, according to the above configuration, occurrence of defects in the resist pattern is also suppressed.
  • the convex portion 201 may have a wider width at the bottom than at the top.
  • reinforcing may include forming a water-soluble film M on the side surface of the convex portion 201.
  • the water-soluble film M supports the convex portions 201, so that pattern collapse of the convex portions can be effectively prevented.
  • reinforcing may include forming a water-soluble film M that connects the lower ends of adjacent convex portions 201.
  • the protrusions 201 are supported by the water-soluble film that connects the lower ends of adjacent protrusions 201, so that pattern collapse of the protrusions 201 can be effectively prevented.
  • crosslinking of the resist may be promoted in the intermediate exposure region 201a on the side surface of the convex portion 201.
  • the resist becomes stronger by promoting crosslinking in the resist in the intermediate exposure region 201a, so that pattern collapse of the convex portions 201 can be effectively prevented.
  • Reinforcing may include supplying a water-soluble material liquid containing a water-soluble material to the recess 202 and solidifying the water-soluble material liquid.
  • the water-soluble material liquid may be supplied to such an extent that the upper portions of the convex portions 201 are not covered. Such a configuration prevents the convex portion 201 from falling down due to the water-soluble material liquid when the water-soluble material liquid is supplied to the recess 202 .
  • Solidifying the water-soluble material liquid may include adjusting the concentration of the water-soluble material liquid so that it is thicker at the bottom than at the top. With such a configuration, solidification of the water-soluble material below the water-soluble material liquid progresses more quickly, so that reinforcement by the water-soluble material can be performed more reliably.
  • Forming the uneven pattern involves forming a first treated film 205 using a resist on the substrate, curing the first treated film 205, and performing a second treatment using a resist on the hardened first treated film 205.
  • the method may include forming the film 206, forming a concavo-convex pattern by exposure treatment and development treatment, and curing the concave-convex pattern.
  • forming the uneven pattern includes heating the substrate on which the uneven pattern is formed, and performing a curing process for the protrusions 201 means heating the substrate on which the uneven pattern including the reinforced protrusions 201 is formed. may include heating.
  • the processing conditions for heating the substrate in performing the curing process of the convex portions 201 are the processing conditions for heating the substrate in forming the uneven pattern, and the cumulative amount of heat applied to the uneven pattern. , may be determined based on. With this configuration, even if the processing conditions for heating the substrate for forming the uneven pattern change, the curing process of the convex portions 201 can be performed while taking into consideration the cumulative amount of heat given to the uneven pattern. Since it is possible to determine the processing conditions for heating the substrate in performing this process, it is possible to suppress fluctuations in the amount of heat applied to the concavo-convex pattern.
  • the configurations of the development unit U3 and heat treatment unit U4 described above are merely examples, and may be changed as appropriate.
  • the process for reinforcing the convex portion 201 and the process for curing it can be changed as appropriate. Further, depending on the shape, width, etc. of the convex portion 201, the methods described above may be combined and executed.
  • the curing process is performed with the convex portions reinforced by supplying the water-soluble material liquid, the pattern collapse of the convex portions is prevented. Further, since the reinforced portion is removed after the hardening process of the convex portion, problems caused by remaining water-soluble materials are also prevented. Therefore, according to the above configuration, occurrence of defects in the resist pattern is also suppressed.
  • the above configuration further prevents the protrusions from collapsing when reinforcing the protrusions by supplying a water-soluble material liquid and when curing the protrusions, resulting in damage to the resist pattern. is further suppressed.
  • the resist becomes stronger by promoting crosslinking in the resist in the intermediate exposure region, so that pattern collapse of the convex portions can be effectively prevented.
  • the reinforcing includes supplying a water-soluble material liquid containing the water-soluble material to the recess and solidifying the water-soluble material liquid, and the water-soluble material liquid is supplied to the recess.
  • the substrate processing method according to any one of [1] to [5], wherein in supplying the water-soluble material liquid, the water-soluble material liquid is supplied to an extent that the upper part of the convex part is not covered.
  • the above configuration prevents the convex portion from falling down due to the water-soluble material liquid when the water-soluble material liquid is supplied to the recessed portion.
  • Forming the uneven pattern includes forming a first treated film of resist on the substrate, curing the first treated film, and applying resist on the first treated film after hardening.
  • Forming the uneven pattern includes heating the substrate on which the uneven pattern is formed, and performing a hardening treatment on the convex portions means that the uneven pattern including the convex portions after reinforcement is heated.
  • the processing conditions for heating the substrate in the curing process of the convex portion include heating the formed substrate, and the processing conditions for heating the substrate in forming the uneven pattern. , and an integrated amount of heat applied to the uneven pattern, the substrate processing method according to any one of [1] to [8].
  • the processing conditions for heating the substrate for forming the uneven pattern change even if the processing conditions for heating the substrate for forming the uneven pattern change, the hardening process of the convex portions is performed while considering the cumulative amount of heat applied to the uneven pattern.
  • the processing conditions for heating the substrate can be determined. Therefore, it is possible to suppress fluctuations in the amount of heat applied to the uneven pattern.
  • a computer-readable storage medium recording a program for causing an apparatus to execute the substrate processing method according to any one of [1] to [9].
  • a development processing section that forms a concavo-convex pattern using a resist on a substrate, a reinforcing processing section that reinforces the convex portions by supplying a water-soluble material liquid to the concave portions of the concavo-convex pattern, and hardening of the convex portions.
  • a substrate processing apparatus comprising: a hardening processing section that performs processing; and a removal processing section that removes a part of the uneven pattern including the portion reinforced in the hardening processing section.
  • the hardening process of the convex portions of the uneven pattern is performed while the convex portions are reinforced by supplying the water-soluble material liquid, so that pattern collapse of the convex portions is prevented. Further, since the reinforced portion is removed after the hardening process of the convex portion, problems caused by remaining water-soluble materials are also prevented. Therefore, according to the above configuration, occurrence of defects in the resist pattern is also suppressed.
  • Substrate processing system (substrate processing apparatus), 2... Coating/developing device (substrate processing apparatus), 3... Exposure device, 20... Rotation holding part, 21... Rotation drive part, 22... Shaft, 23... Holding part, 30a , 30b, 30c...Liquid supply unit, 31...Liquid source, 33...Valve, 34...Nozzle, 35...Piping, 40...Chamber, 43...Holding unit, 44...Hot plate, 45...Heater, 46...Support pin, 47 ...Drive part.

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PCT/JP2023/020108 2022-06-08 2023-05-30 基板処理方法、記憶媒体、及び基板処理装置 WO2023238737A1 (ja)

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Citations (6)

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Publication number Priority date Publication date Assignee Title
WO2004111734A1 (ja) * 2003-06-11 2004-12-23 Tokyo Ohka Kogyo Co., Ltd. ポジ型レジスト組成物、レジスト積層体、およびレジストパターン形成方法
WO2009008265A1 (ja) * 2007-07-11 2009-01-15 Az Electronic Materials (Japan) K.K. 微細パターン形成用組成物およびそれを用いた微細パターン形成方法
JP2015023172A (ja) * 2013-07-19 2015-02-02 東京エレクトロン株式会社 基板処理装置、基板処理方法及び基板処理用記録媒体
WO2015080061A1 (ja) * 2013-11-29 2015-06-04 旭硝子株式会社 コーティング用組成物およびフォトレジスト積層体の製造方法
WO2015129405A1 (ja) * 2014-02-26 2015-09-03 日産化学工業株式会社 レジストパターンに塗布されるポリマー含有塗布液
JP2017165846A (ja) * 2016-03-15 2017-09-21 アーゼッド・エレクトロニック・マテリアルズ（ルクセンブルグ）ソシエテ・ア・レスポンサビリテ・リミテ 微細パターン形成用組成物およびそれを用いた微細パターン形成方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004111734A1 (ja) * 2003-06-11 2004-12-23 Tokyo Ohka Kogyo Co., Ltd. ポジ型レジスト組成物、レジスト積層体、およびレジストパターン形成方法
WO2009008265A1 (ja) * 2007-07-11 2009-01-15 Az Electronic Materials (Japan) K.K. 微細パターン形成用組成物およびそれを用いた微細パターン形成方法
JP2015023172A (ja) * 2013-07-19 2015-02-02 東京エレクトロン株式会社 基板処理装置、基板処理方法及び基板処理用記録媒体
WO2015080061A1 (ja) * 2013-11-29 2015-06-04 旭硝子株式会社 コーティング用組成物およびフォトレジスト積層体の製造方法
WO2015129405A1 (ja) * 2014-02-26 2015-09-03 日産化学工業株式会社 レジストパターンに塗布されるポリマー含有塗布液
JP2017165846A (ja) * 2016-03-15 2017-09-21 アーゼッド・エレクトロニック・マテリアルズ（ルクセンブルグ）ソシエテ・ア・レスポンサビリテ・リミテ 微細パターン形成用組成物およびそれを用いた微細パターン形成方法

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