WO2014038420A1 - Substrate processing method, computer storage medium, and substrate processing system - Google Patents

Abstract

The present invention is a method which processes a substrate, using a block copolymer including a first polymer and a second polymer, wherein: a neutral layer having an intermediate affinity with respect to the first polymer and the second polymer is formed upon a substrate; with respect to the substrate whereupon a resist layer is formed upon the neutral layer, an exposed face of the neutral layer which is exposed from the resist layer is surface processed; thereafter, with respect to the substrate whereupon the resist pattern has been removed, a block copolymer is coated upon the neutral layer; and the block copolymer upon the neutral layer is phase separated into the first polymer and the second polymer.

Description

Substrate processing method, computer storage medium, and substrate processing system

This application claims priority based on Japanese Patent Application No. 2012-196737 filed in Japan on September 7, 2012, the contents of which are incorporated herein by reference.
The present invention relates to a substrate processing method, a computer storage medium, and a substrate processing system using a block copolymer including a hydrophilic polymer having hydrophilicity and a hydrophobic polymer having hydrophobicity.

For example, in the manufacturing process of a semiconductor device, for example, a resist coating process for coating a resist solution on a semiconductor wafer (hereinafter referred to as “wafer”) to form a resist film, an exposure process for exposing a predetermined pattern on the resist film, A photolithography process for sequentially performing a development process for developing the exposed resist film is performed to form a predetermined resist pattern on the wafer. Then, using the resist pattern as a mask, an etching process is performed on the film to be processed on the wafer, and then a resist film removing process is performed to form a predetermined pattern on the film to be processed.

Incidentally, in recent years, in order to further increase the integration of semiconductor devices, it is required to make the pattern of the film to be processed finer. For this reason, miniaturization of the resist pattern has been advanced, and for example, the light of the exposure process in the photolithography process has been shortened. However, there are technical and cost limitations to shortening the wavelength of the exposure light source, and it is difficult to form a fine resist pattern on the order of several nanometers, for example, only by the method of advancing the wavelength of light. is there.

Therefore, a wafer processing method using a block copolymer containing a hydrophilic polymer having hydrophilicity and a hydrophobic polymer having hydrophobicity has been proposed (Non-Patent Document 1). In this method, a resist pattern is first formed on the antireflection film of the wafer, and then a neutral layer having an intermediate affinity for the hydrophilic polymer and the hydrophobic polymer is formed on the antireflection film and the resist pattern. To do. Thereafter, the neutral layer on the resist pattern is removed together with the resist pattern, and a pattern of the neutral layer 601 is formed on the antireflection film 600 of the wafer W as shown in FIG. Thereafter, as shown in FIG. 29, a block copolymer 610 is applied on the antireflection film 600 and the neutral layer 601, and the hydrophilic polymer 611 and the hydrophobic polymer 612 are phase-separated from the block copolymer 610. At this time, since the antireflection film 600 has hydrophilicity, on the antireflection film 600, for example, a hydrophobic polymer 612, a hydrophilic polymer 611, and a hydrophobic polymer 612 are separated in this order. Thereafter, for example, the hydrophilic polymer 611 is removed, whereby a fine pattern of the hydrophobic polymer 612 is formed on the wafer W. Then, the film to be processed is etched using the pattern of the hydrophobic polymer 612 as a mask, and a predetermined pattern is formed on the film to be processed.

However, when the wafer processing method described in Non-Patent Document 1 is used, a portion where the antireflection film 600 is exposed in the neutral layer 601 is recessed on the wafer W as shown in FIG. When there is such a step, in the block copolymer 610 applied on the wafer W as shown in FIG. 29, the height of the pattern of the hydrophilic polymer 611 becomes non-uniform in the wafer surface. Then, after removing the hydrophilic polymer 611 from the block copolymer 610, the etching depth in the wafer surface becomes non-uniform when etching the film to be processed using the pattern of the hydrophobic polymer 612 as a mask. For this reason, the etching process of a to-be-processed film cannot be performed appropriately, and a predetermined pattern may not be appropriately formed in a to-be-processed film.

The present invention has been made in view of such points, and an object of the present invention is to appropriately form a predetermined pattern on a substrate in substrate processing using a block copolymer containing a hydrophilic polymer and a hydrophobic polymer. And

To achieve the above object, the present invention provides a method for treating a substrate using a block copolymer comprising a first polymer and a second polymer, wherein the first polymer and the second polymer are processed. A neutral layer forming step for forming a neutral layer having an intermediate affinity for the polymer on the substrate, and the substrate on which the resist pattern is formed on the neutral layer, exposed from the resist pattern Applying the block copolymer onto the neutral layer on the neutral layer treatment step for surface-treating the exposed surface of the neutral layer and the substrate from which the resist pattern has been removed after the neutral layer treatment step A block copolymer coating step, and a polymer separation step of phase-separating the block copolymer on the neutral layer into the first polymer and the second polymer.

According to the present invention, in the neutral layer processing step, the exposed surface of the neutral layer exposed from the resist pattern is surface-treated, and the surface of the neutral layer is kept flat. If it does so, even if a block copolymer is apply | coated on a neutral layer in a subsequent block copolymer application | coating process, the surface of the said block copolymer will be formed flat. Therefore, the pattern height of the hydrophilic polymer or the hydrophobic polymer formed on the substrate by performing the polymer separating step and the polymer removing step thereafter can be made uniform. Since a predetermined fine pattern can be appropriately formed on the substrate in this way, the film to be processed can be appropriately etched using the hydrophilic polymer or hydrophobic polymer pattern as a mask. A predetermined pattern can be formed on the treatment film.

Another aspect of the present invention is a readable computer storage medium storing a program that operates on a computer of a control unit that controls the substrate processing system so that the substrate processing method is executed by the substrate processing system.

According to yet another aspect, the present invention provides a system for processing a substrate using a block copolymer including a first polymer and a second polymer, wherein the first polymer and the second polymer are combined with each other. A neutral layer forming apparatus for forming a neutral layer having an intermediate affinity on the substrate, and the neutral layer exposed from the resist pattern with respect to the substrate on which the resist pattern is formed on the neutral layer A neutral layer processing apparatus for surface-treating an exposed surface of a layer; and the block copolymer for the substrate from which the resist pattern is removed after the exposed surface is surface-treated by the neutral layer processing apparatus. A block copolymer coating device for coating on a neutral layer; a polymer separation device for phase-separating the block copolymer on the neutral layer into the first polymer and the second polymer;
Have

According to the present invention, a predetermined pattern can be appropriately formed on a substrate in substrate processing using a block copolymer containing a hydrophilic polymer and a hydrophobic polymer.

It is explanatory drawing which shows the outline of a structure of the substrate processing system concerning this Embodiment. It is a top view which shows the outline of a structure of a coating-development processing apparatus. It is a side view which shows the outline of the internal structure of a coating and developing treatment apparatus. It is a side view which shows the outline of the internal structure of a coating and developing treatment apparatus. It is a top view which shows the outline of a structure of an etching processing apparatus. It is the flowchart explaining the main processes of wafer processing. It is explanatory drawing of the longitudinal cross-section which shows a mode that the antireflection film and the neutral layer were formed on the wafer. It is explanatory drawing of the longitudinal cross-section which shows a mode that the resist pattern was formed on the wafer. It is explanatory drawing of the longitudinal cross-section which shows a mode that the exposed surface of the neutral layer on a wafer was hydrophilized. It is explanatory drawing of the longitudinal cross-section which shows a mode that the resist pattern was removed. It is explanatory drawing of the longitudinal cross-section which shows a mode that the block copolymer was apply | coated on the wafer. It is explanatory drawing of the longitudinal cross-section which shows a mode that the block copolymer was phase-separated into the hydrophilic polymer and the hydrophobic polymer. It is explanatory drawing of the plane which shows a mode that the block copolymer was phase-separated into the hydrophilic polymer and the hydrophobic polymer. It is explanatory drawing of the longitudinal cross-section which shows a mode that the hydrophobic polymer was removed. It is a side view which shows the outline of the internal structure of the coating-development processing apparatus concerning other embodiment. It is explanatory drawing of the longitudinal cross-section which shows a mode that the hydrophilic film was formed on the wafer. It is explanatory drawing of the longitudinal cross-section which shows a mode that the hydrophilic film on a resist pattern and a resist pattern was removed. It is a side view which shows the outline of the internal structure of the coating-development processing apparatus concerning other embodiment. It is explanatory drawing of the longitudinal cross-section which shows a mode that the block copolymer was phase-separated into the hydrophilic polymer and the hydrophobic polymer. It is explanatory drawing of the plane which shows a mode that the block copolymer was phase-separated into the hydrophilic polymer and the hydrophobic polymer orthogonal to the longitudinal direction of the hydrophilic region. It is explanatory drawing which shows a mode that the resist pattern was reflowed. It is the figure which imaged the plane state of the reflowed resist pattern. It is explanatory drawing of the longitudinal cross-section which shows a mode that the exposed surface of the neutral layer on a wafer was hydrophilized after reflow. It is explanatory drawing of the longitudinal cross-section which shows a mode that the block copolymer was phase-separated into the hydrophilic polymer and the hydrophobic polymer. It is explanatory drawing of the longitudinal cross-section which shows a mode that the hydrophilic film was formed on the wafer after reflow. It is explanatory drawing of the plane which shows a mode that the resist pattern was formed on the wafer in other embodiment. It is explanatory drawing of the plane which shows a mode that the block copolymer was phase-separated into the hydrophilic polymer and the hydrophobic polymer in other embodiment. It is explanatory drawing of the longitudinal cross-section which shows a mode that the pattern of the neutral layer was formed on the wafer in the conventional wafer process. It is explanatory drawing of the longitudinal cross-section which shows a mode that the block copolymer was phase-separated into the hydrophilic polymer and the hydrophobic polymer in the conventional wafer process.

Hereinafter, embodiments of the present invention will be described. FIG. 1 is an explanatory diagram showing an outline of a configuration of a substrate processing system 1 according to the present embodiment.

As shown in FIG. 1, the substrate processing system 1 includes a coating and developing apparatus 2 that performs photolithography processing on a wafer as a substrate, and an etching processing apparatus 3 that performs etching processing on the wafer. A film to be processed (not shown) is formed in advance on the wafer processed by the substrate processing system 1.

As shown in FIG. 2, the coating / developing apparatus 2 includes, for example, a cassette station 10 in which a cassette C containing a plurality of wafers W is carried in and out of the outside, and a predetermined type of sheet processing in a photolithography process. A processing station 11 having a plurality of various processing apparatuses for processing and an interface station 13 for transferring the wafer W between the exposure apparatus 12 adjacent to the processing station 11 are integrally connected. .

The cassette station 10 is provided with a cassette mounting table 20. The cassette mounting table 20 is provided with a plurality of, for example, four cassette mounting plates 21. The cassette mounting plates 21 are arranged in a line in the horizontal X direction (vertical direction in FIG. 2). The cassette C can be placed on these cassette placement plates 21 when the cassette C is carried in and out of the coating and developing treatment apparatus 2.

As shown in FIG. 2, the cassette station 10 is provided with a wafer transfer device 23 that is movable on a transfer path 22 extending in the X direction. The wafer transfer device 23 is also movable in the vertical direction and the vertical axis direction (θ direction), and includes a cassette C on each cassette mounting plate 21 and a delivery device for a third block G3 of the processing station 11 described later. The wafer W can be transferred between the two.

The processing station 11 is provided with a plurality of, for example, four blocks G1, G2, G3, and G4 having various devices. For example, the first block G1 is provided on the front side of the processing station 11 (X direction negative direction side in FIG. 2), and the second side is provided on the back side of the processing station 11 (X direction positive direction side in FIG. 2). Block G2 is provided. Further, a third block G3 is provided on the cassette station 10 side (Y direction negative direction side in FIG. 1) of the processing station 11, and the interface station 13 side (Y direction positive direction side in FIG. 2) of the processing station 11 is provided. Is provided with a fourth block G4.

For example, in the first block G1, as shown in FIG. 3, a plurality of liquid processing apparatuses, for example, a developing apparatus 30 for developing the wafer W, and a cleaning apparatus 31 for cleaning the wafer W by coating the wafer W with an organic solvent. An antireflection film forming device 32 for forming an antireflection film on the wafer W, a neutral layer forming device 33 for applying a neutral agent on the wafer W to form a neutral layer, and a resist solution on the wafer W Then, a resist coating device 34 for forming a resist film and a block copolymer coating device 35 for coating a block copolymer on the wafer W are stacked in order from the bottom.

For example, the developing device 30, the cleaning device 31, the antireflection film forming device 32, the neutral layer forming device 33, the resist coating device 34, and the block copolymer coating device 35 are arranged side by side in the horizontal direction. The number and arrangement of the developing device 30, the cleaning device 31, the antireflection film forming device 32, the neutral layer forming device 33, the resist coating device 34, and the block copolymer coating device 35 can be arbitrarily selected.

In the developing device 30, the cleaning device 31, the antireflection film forming device 32, the neutral layer forming device 33, the resist coating device 34, and the block copolymer coating device 35, for example, a spin for applying a predetermined coating solution onto the wafer W. Coating is performed. In spin coating, for example, a coating liquid is discharged onto the wafer W from a coating nozzle, and the wafer W is rotated to diffuse the coating liquid to the surface of the wafer W.

Note that the block copolymer applied onto the wafer W by the block copolymer coating device 35 includes a first polymer and a second polymer. A hydrophobic polymer having hydrophobicity (nonpolar) is used as the first polymer, and a hydrophilic polymer having hydrophilicity (polarity) is used as the second polymer. In the present embodiment, for example, polymethyl methacrylate (PMMA) is used as the hydrophilic polymer, and for example, polystyrene (PS) is used as the hydrophobic polymer. The ratio of the molecular weight of the hydrophilic polymer in the block copolymer is 40% to 60%, and the ratio of the molecular weight of the hydrophobic polymer in the block copolymer is 60% to 40%. The block copolymer is a polymer obtained by linearly combining these hydrophilic polymer and hydrophobic polymer.

Further, the neutral layer formed on the wafer W by the neutral layer forming apparatus 33 has an intermediate affinity for the hydrophilic polymer and the hydrophobic polymer. In the present embodiment, for example, a random copolymer or an alternating copolymer of polymethyl methacrylate and polystyrene is used as the neutral layer. In the following, the term “neutral” means having an intermediate affinity for the hydrophilic polymer and the hydrophobic polymer.

For example, in the second block G2, as shown in FIG. 4, a heat treatment apparatus 40 that performs heat treatment of the wafer W, and a neutral layer treatment that performs surface treatment of the neutral layer by irradiating the neutral layer on the wafer W with ultraviolet rays. An ultraviolet irradiation device 41 as an apparatus, an adhesion device 42 for hydrophobizing the wafer W, and a peripheral exposure device 43 for exposing the outer periphery of the wafer W are provided side by side in the vertical and horizontal directions. The heat treatment apparatus 40 includes a hot plate for placing and heating the wafer W and a cooling plate for placing and cooling the wafer W, and can perform both heat treatment and cooling treatment. The ultraviolet irradiation device 41 includes a mounting table on which the wafer W is mounted, and an ultraviolet irradiation unit that irradiates the wafer W on the mounting table with ultraviolet light having a wavelength of 172 nm, for example. Among the plurality of heat treatment apparatuses 40, some of the heat treatment apparatuses 40 are polymers that cause the block copolymer coated on the wafer W by the block copolymer coating apparatus 35 to phase-separate into a hydrophilic polymer and a hydrophobic polymer. Functions as a separation device. Further, the number and arrangement of the heat treatment apparatus 40, the ultraviolet irradiation apparatus 41, the adhesion apparatus 42, and the peripheral exposure apparatus 43 can be arbitrarily selected.

For example, in the third block G3, a plurality of delivery devices 50, 51, 52, 53, 54, 55, 56 are provided in order from the bottom. The fourth block G4 is provided with a plurality of delivery devices 60, 61, 62 in order from the bottom.

As shown in FIG. 1, a wafer transfer area D is formed in an area surrounded by the first block G1 to the fourth block G4. For example, a wafer transfer device 70 is disposed in the wafer transfer region D.

The wafer transfer device 70 has, for example, a transfer arm that is movable in the Y direction, the X direction, the θ direction, and the vertical direction. The wafer transfer device 70 moves in the wafer transfer area D and transfers the wafer W to a predetermined device in the surrounding first block G1, second block G2, third block G3, and fourth block G4. it can.

For example, as shown in FIG. 4, a plurality of wafer transfer apparatuses 70 are arranged in the vertical direction, and can transfer the wafer W to a predetermined apparatus having the same height of each of the blocks G1 to G4, for example.

Further, in the wafer transfer area D, a shuttle transfer device 80 that transfers the wafer W linearly between the third block G3 and the fourth block G4 is provided.

The shuttle transport device 80 is linearly movable in the Y direction, for example. The shuttle transfer device 80 moves in the Y direction while supporting the wafer W, and can transfer the wafer W between the transfer device 52 of the third block G3 and the transfer device 62 of the fourth block G4.

As shown in FIG. 1, a wafer transfer device 100 is provided next to the third block G3 on the positive side in the X direction. The wafer transfer apparatus 100 has a transfer arm that is movable in the X direction, the θ direction, and the vertical direction, for example. The wafer transfer device 100 can move up and down while supporting the wafer W, and can transfer the wafer W to each delivery device in the third block G3.

The interface station 13 is provided with a wafer transfer device 110 and a delivery device 111. The wafer transfer device 110 has a transfer arm that is movable in the Y direction, the θ direction, and the vertical direction, for example. The wafer transfer device 110 can transfer the wafer W between each transfer device, the transfer device 111, and the exposure device 12 in the fourth block G4, for example, by supporting the wafer W on a transfer arm.

As shown in FIG. 5, the etching processing apparatus 3 includes a cassette station 200 that carries the wafer W into and out of the etching processing apparatus 3, a common transport unit 201 that transports the wafer W, and a block copolymer that is phase-separated on the wafer W. Etching apparatus 202, 203 as polymer removing apparatuses for selectively removing either hydrophilic polymer or hydrophobic polymer, and etching apparatus 204 for etching a film to be processed on wafer W into a predetermined pattern , 205.

The cassette station 200 has a transfer chamber 211 in which a wafer transfer mechanism 210 for transferring the wafer W is provided. The wafer transfer mechanism 210 has two transfer arms 210a and 210b that hold the wafer W substantially horizontally, and is configured to transfer the wafer W while holding it by either of the transfer arms 210a and 210b. . A cassette mounting table 212 on which a cassette C capable of accommodating a plurality of wafers W arranged side by side is mounted on the side of the transfer chamber 211. In the illustrated example, a plurality of, for example, three cassettes C can be mounted on the cassette mounting table 212.

The transfer chamber 211 and the common transfer unit 201 are connected to each other via two load lock devices 213a and 213b that can be evacuated.

The common transfer unit 201 includes a transfer chamber chamber 214 having a sealable structure formed to have a substantially polygonal shape (in the illustrated example, a hexagonal shape) as viewed from above, for example. In the transfer chamber 214, a wafer transfer mechanism 215 for transferring the wafer W is provided. The wafer transfer mechanism 215 has two transfer arms 215a and 215b that hold the wafer W substantially horizontally, and is configured to transfer the wafer W while holding the wafer W by either of the transfer arms 215a and 215b. .

Etching devices 202, 203, 204, 205 and load lock devices 213 b, 213 a are arranged outside the transfer chamber chamber 214 so as to surround the periphery of the transfer chamber chamber 214. The etching devices 202, 203, 204, 205 and the load lock devices 213b, 213a are arranged in this order in the clockwise direction when viewed from above, for example, and face the six side portions of the transfer chamber 214, respectively. Are arranged.

For example, an RIE (Reactive Ion Etching) apparatus is used as the etching apparatuses 202 to 205, for example. That is, in the etching apparatuses 202 to 205, dry etching for etching the hydrophobic polymer and the film to be processed is performed by reactive gas (etching gas), ions, and radicals.

The substrate processing system 1 described above is provided with a control unit 300 as shown in FIG. The control unit 300 is a computer, for example, and has a program storage unit (not shown). The program storage unit stores a program for controlling the processing of the wafer W in the substrate processing system 1. The program storage unit also stores a program for controlling the operation of driving systems such as the above-described various processing apparatuses and transfer apparatuses to realize a peeling process described later in the substrate processing system 1. The program is recorded on a computer-readable storage medium such as a computer-readable hard disk (HD), flexible disk (FD), compact disk (CD), magnetic optical desk (MO), or memory card. Or installed in the control unit 300 from the storage medium.

Next, wafer processing performed using the substrate processing system 1 configured as described above will be described. FIG. 6 is a flowchart showing an example of main steps of such wafer processing.

First, a cassette C containing a plurality of wafers W is carried into the cassette station 10 of the coating and developing treatment apparatus 2 and placed on a predetermined cassette placing plate 21. Thereafter, the wafers W in the cassette C are sequentially taken out by the wafer transfer device 23 and transferred to the transfer device 53 of the processing station 11.

Next, the wafer W is transferred to the heat treatment apparatus 40 by the wafer transfer apparatus 70 and the temperature is adjusted. Thereafter, the wafer W is transferred to the antireflection film forming apparatus 32 by the wafer transfer apparatus 70, and an antireflection film 400 is formed on the wafer W as shown in FIG. 7 (step S1 in FIG. 6). Thereafter, the wafer W is transferred to the heat treatment apparatus 40, heated, and the temperature is adjusted.

Next, the wafer W is transferred to the neutral layer forming device 33 by the wafer transfer device 70. In the neutral layer forming apparatus 33, as shown in FIG. 7, a neutral agent is applied on the antireflection film 400 of the wafer W to form a neutral layer 401 (step S2 in FIG. 6). Thereafter, the wafer W is transferred to the heat treatment apparatus 40, heated, temperature-controlled, and then returned to the delivery apparatus 53.

Next, the wafer W is transferred to the delivery device 54 by the wafer transfer device 100. Thereafter, the wafer W is transferred to the adhesion device 42 by the wafer transfer device 70 and subjected to an adhesion process. Thereafter, the wafer W is transferred to the resist coating device 34 by the wafer transfer device 70, and a resist solution is applied onto the neutral layer 401 of the wafer W to form a resist film. Thereafter, the wafer W is transferred to the heat treatment apparatus 40 by the wafer transfer apparatus 70 and pre-baked. Thereafter, the wafer W is transferred to the delivery device 55 by the wafer transfer device 70.

Next, the wafer W is transferred to the peripheral exposure device 43 by the wafer transfer device 70 and subjected to peripheral exposure processing. Thereafter, the wafer W is transferred to the delivery device 56 by the wafer transfer device 70.

Next, the wafer W is transferred to the transfer device 52 by the wafer transfer device 100 and transferred to the transfer device 62 by the shuttle transfer device 80.

Thereafter, the wafer W is transferred to the exposure apparatus 12 by the wafer transfer apparatus 110 of the interface station 13 and subjected to exposure processing.

Next, the wafer W is transferred from the exposure apparatus 12 to the delivery apparatus 60 by the wafer transfer apparatus 110. Thereafter, the wafer W is transferred to the heat treatment apparatus 40 by the wafer transfer apparatus 70 and subjected to post-exposure baking. Thereafter, the wafer W is transferred to the developing device 30 by the wafer transfer device 70 and developed. After the development is completed, the wafer W is transferred to the heat treatment apparatus 40 by the wafer transfer apparatus 70 and subjected to a post-bake process. Thus, a predetermined resist pattern 402 is formed on the neutral layer 401 of the wafer W as shown in FIG. 8 (step S3 in FIG. 6). In this embodiment, the resist pattern 402 has a linear shape in plan view. It has a line portion 402a and a linear space portion 402b, and is a so-called line-and-space resist pattern. The width of the space portion 402b is set so that the hydrophilic polymer 405 and the hydrophobic polymer 406 are alternately arranged in the odd number layers in the space portion 402b as described later.

The wafer W on which the resist pattern 402 is formed is transferred to the ultraviolet irradiation device 41 by the wafer transfer device 70. In the ultraviolet irradiation device 41, as shown in FIG. 9, the exposed surface of the neutral layer 401 exposed from the resist pattern 402 (space portion 402b) is irradiated with ultraviolet rays. At this time, ultraviolet rays having a wavelength of 172 nm are irradiated. Then, the exposed surface of the neutral layer 401 is oxidized and hydrophilized (step S4 in FIG. 6). Hereinafter, the region of the neutral layer 401 thus made hydrophilic may be referred to as a hydrophilic region 403.

In addition, as a result of intensive studies by the inventors, it has been found that the wavelength of ultraviolet rays for forming the hydrophilic region 403 in the neutral layer 401 may be 300 nm or less. Specifically, when an ultraviolet ray having a wavelength of 300 nm or less is irradiated, active oxygen can be generated from oxygen in the processing atmosphere, and the exposed surface of the neutral layer 401 is oxidized and hydrophilized by this active oxygen. In addition, in order to generate | occur | produce active oxygen more easily, it turns out that it is better to use ozone as a process atmosphere. In particular, when the wavelength of ultraviolet rays is 172 nm, not only when ozone is used as a processing atmosphere, but also when the processing atmosphere is an air atmosphere, active oxygen can be efficiently generated from oxygen in the air atmosphere. I know it.

Next, the wafer W is transferred to the cleaning device 31 by the wafer transfer device 70. In the cleaning device 31, an organic solvent is supplied onto the wafer W, and the resist pattern 402 on the wafer W is removed as shown in FIG. 10 (step S5 in FIG. 6). Then, in the neutral layer 401, the surface of the hydrophilic region 403 has hydrophilicity, and the surface of other regions has neutrality. And the surface of the neutral layer 401 is maintained flat. Thereafter, the wafer W is transferred to the delivery device 50 by the wafer transfer device 70.

Next, the wafer W is transferred to the delivery device 55 by the wafer transfer device 100. Thereafter, the wafer W is transferred to the block copolymer coating device 35 by the wafer transfer device 70. In the block copolymer coating device 35, the block copolymer 404 is coated on the neutral layer 401 of the wafer W as shown in FIG. 11 (step S6 in FIG. 6). At this time, since the surface of the neutral layer 401 is kept flat, the block copolymer 404 is also applied so as to have a uniform film thickness.

Next, the wafer W is transferred to the heat treatment apparatus 40 by the wafer transfer apparatus 70. In the heat treatment apparatus 40, a heat treatment at a predetermined temperature is performed on the wafer W. Then, as shown in FIGS. 12 and 13, the block copolymer 404 on the wafer W is phase-separated into the hydrophilic polymer 405 and the hydrophobic polymer 406 (step S7 in FIG. 6).

Here, as described above, in the block copolymer 404, the molecular weight ratio of the hydrophilic polymer 405 is 40% to 60%, and the molecular weight ratio of the hydrophobic polymer 406 is 60% to 40%. Then, in step S6, as shown in FIGS. 12 and 13, the hydrophilic polymer 405 and the hydrophobic polymer 406 are phase-separated into a lamellar structure. In addition, since the width of the space portion 402b of the resist pattern 402 is formed to a predetermined width in the above-described step S3, the hydrophilic polymer 405 and the hydrophobic polymer 406 are formed on the hydrophilic region 403 of the neutral layer 401. Alternatingly arranged in odd layers, for example, three layers. Specifically, since the surface of the hydrophilic region 403 has hydrophilicity, the hydrophilic polymer 405 is disposed in the middle on the hydrophilic region 403, and the hydrophobic polymers 406 and 406 are disposed on both sides thereof. And the hydrophilic polymer 405 and the hydrophobic polymer 406 are alternately arrange | positioned also on the other area | region of the neutral layer 401. FIG.

Thereafter, the wafer W is transferred to the delivery device 50 by the wafer transfer device 70, and then transferred to the cassette C of the predetermined cassette mounting plate 21 by the wafer transfer device 23 of the cassette station 10.

When predetermined processing is performed on the wafer W in the coating and developing treatment apparatus 2, the cassette C containing the wafer W is unloaded from the coating and developing treatment apparatus 2 and then loaded into the etching processing apparatus 3.

In the etching processing apparatus 3, first, one wafer W is taken out from the cassette C on the cassette mounting table 212 by the wafer transfer mechanism 210 and loaded into the load lock apparatus 213 a. When the wafer W is loaded into the load lock device 213a, the inside of the load lock device 213a is sealed and decompressed. After that, the inside of the load lock device 213a and the inside of the transfer chamber chamber 214 in a state where the pressure is reduced with respect to the atmospheric pressure (for example, a substantially vacuum state) are communicated. Then, the wafer transfer mechanism 215 unloads the wafer W from the load lock device 213a and loads it into the transfer chamber 214.

The wafer W carried into the transfer chamber 214 is then transferred to the etching apparatus 202 by the wafer transfer mechanism 215. In the etching apparatus 202, the wafer W is etched, and the hydrophilic polymer 405 is selectively removed as shown in FIG. 14 to form a predetermined pattern of the hydrophobic polymer 406 (step S8 in FIG. 6). At this time, since the film thickness of the block copolymer 404 is uniform, the pattern height of the hydrophobic polymer 406 is also uniform.

Thereafter, the wafer W is transferred to the etching apparatus 204 by the wafer transfer mechanism 215. In the etching apparatus 204, the film to be processed on the wafer W is etched using the hydrophobic polymer 406 on the wafer W as a mask. Thereafter, the hydrophobic polymer 406 and the antireflection film are removed, and a predetermined pattern is formed on the film to be processed (step S9 in FIG. 6).

Thereafter, the wafer W is returned again into the transfer chamber 214 by the wafer transfer mechanism 215. Then, the wafer is transferred to the wafer transfer mechanism 210 via the load lock device 213b and stored in the cassette C. Thereafter, the cassette C containing the wafers W is unloaded from the etching processing apparatus 3 and a series of wafer processing ends.

According to the above embodiment, in step S4, the exposed surface of the neutral layer 401 exposed from the resist pattern 402 (space portion 402b) is subjected to surface treatment to make it hydrophilic, and the surface of the neutral layer 401 is flattened. Maintained. Then, even if the block copolymer 404 is applied on the neutral layer 401 in the subsequent step S6, the surface of the block copolymer 404 is formed flat. For this reason, the pattern height of the hydrophobic polymer 406 formed on the wafer W by performing the subsequent steps S7 and S8 can be made uniform. As described above, since a predetermined fine pattern of the hydrophobic polymer 406 can be appropriately formed on the wafer W, the etching process of the film to be processed using the pattern as a mask can be appropriately performed in step S9. A predetermined pattern can be formed on the film to be processed.

Here, conventionally, in order to form a hydrophilic region and a neutral region on the wafer W as in step S4, the neutral layer is also etched using the resist pattern as a mask. As a result, the surface from which the neutral layer has been removed has hydrophilicity due to the exposure of the antireflection film, and the surface on which the neutral layer remains has neutrality. However, in this case, in order to etch the neutral layer, the wafer W has to be once taken out of the coating and developing treatment apparatus 2 and transferred to the etching treatment apparatus 3.

In this respect, in step S4 of the present embodiment, in the ultraviolet irradiation device 41 in the coating and developing treatment apparatus 2, the exposed surface of the neutral layer 401 is subjected to surface treatment by ultraviolet irradiation to make it hydrophilic. Accordingly, the transfer of the wafer W from the coating and developing treatment apparatus 2 to the etching treatment apparatus 3 can be omitted. The wafer processing in steps S1 to S7 is performed by one coating and developing processing apparatus 2. Therefore, the throughput of wafer processing in the substrate processing system 1 can be improved.

In addition, since the wavelength of ultraviolet light applied to the exposed surface of the neutral layer 401 in step S4 is 172 nm, active oxygen is efficiently generated from oxygen in the air atmosphere as compared with the case of using ultraviolet light with other wavelengths. be able to. Therefore, the exposed surface of the neutral layer 401 can be more easily made hydrophilic.

The resist pattern 402 formed in step S3 is a line-and-space resist pattern. The molecular weight ratio of the hydrophilic polymer 405 in the block copolymer 404 is 40% to 60%. The molecular weight of the hydrophobic polymer 406 is Therefore, in step S7, the block copolymer 404 can be phase-separated into a hydrophilic polymer 405 and a hydrophobic polymer 406 in a lamellar structure. Moreover, since the width of the space portion 402b of the resist pattern 402 is formed to a predetermined width in the above-described step S3, the hydrophilic polymer 405 and the hydrophobic polymer 406 are formed on the hydrophilic region 403 of the neutral layer 401. Alternatingly arranged in odd layers, for example, three layers. Then, the hydrophilic polymer 405 and the hydrophobic polymer 406 can be formed on the wafer W with an appropriate lamellar structure.

In the above embodiment, the exposed surface of the neutral layer 401 is irradiated with ultraviolet rays in step S4 to make the exposed surface hydrophilic, but the means for making the exposed surface hydrophilic is not limited to this. For example, a hydrophilic film having hydrophilicity may be formed on the exposed surface of the neutral layer 401.

In this case, as shown in FIG. 15, the first block G1 of the coating and developing treatment apparatus 2 is provided with a hydrophilic film forming apparatus 500 that forms a hydrophilic film by applying a hydrophilic coating liquid on the wafer W. . The number and arrangement of the hydrophilic film forming apparatuses 500 can be arbitrarily selected. In the hydrophilic film forming apparatus 500, for example, spin coating for applying a predetermined coating liquid on the wafer W is performed as in the other liquid processing apparatuses of the first block G1. The hydrophilic coating solution is not particularly limited, but in this embodiment, for example, a solution in which a hydroxyl group is bonded to polymethyl methacrylate (PMMA-OH) is used.

Then, the wafer W on which the resist pattern 402 is formed in step S3 is transferred to the hydrophilic film forming apparatus 500. In the hydrophilic film forming apparatus 500, as shown in FIG. 16, the coating liquid is applied onto the exposed surface of the neutral layer 401 of the wafer W and the resist pattern 402 to form a hydrophilic film 510. Thereafter, the wafer W is transferred to the heat treatment apparatus 40, heated, and the temperature is adjusted.

Thereafter, in step S5, an organic solvent is supplied onto the wafer W by the cleaning device 31, and the hydrophilic film 510 on the resist pattern 402 is removed together with the resist pattern 402 on the wafer W as shown in FIG. Further, the upper portion of the hydrophilic film 510 on the exposed surface of the neutral layer 401 is also removed. Thus, a thin hydrophilic film 510 having a film thickness of, for example, 5 nm is formed only on the exposed surface of the neutral layer 401. Although the hydrophilic film 510 can be visually recognized in the illustrated example, the thickness of the hydrophilic film 510 is actually smaller than the thickness of the neutral layer 401 and the surface of the neutral layer 401 is kept flat. ing.

Note that the other steps S1 to S3 and S6 to S9 are the same as those in the above embodiment, and the description thereof is omitted.

According to this embodiment, since the thin hydrophilic film 510 can be formed on the exposed surface of the neutral layer 401, the exposed surface can be hydrophilized. Therefore, the same effect as that of the above embodiment can be enjoyed. That is, a predetermined fine pattern of the hydrophilic polymer 405 can be appropriately formed on the wafer W, and the processing target film can be appropriately etched using the pattern as a mask in step S9. Further, the throughput of wafer processing in the substrate processing system 1 can be improved.

In the above embodiment, the exposed surface of the neutral layer 401 is hydrophilized as the surface treatment in the step S4. However, as the surface treatment, the exposed surface may be hydrophobized.

In such a case, as shown in FIG. 18, the first block G1 of the coating and developing treatment apparatus 2 is provided with a hydrophobic film forming apparatus 550 that forms a hydrophobic film by applying a hydrophobic coating liquid onto the wafer W. . The number and arrangement of the hydrophobic film forming apparatuses 550 can be arbitrarily selected. In the hydrophobic film forming apparatus 550, for example, spin coating for applying a predetermined coating liquid onto the wafer W is performed as in the other liquid processing apparatuses of the first block G1. The hydrophobic coating liquid is not particularly limited, but in this embodiment, for example, a liquid in which a hydroxyl group is bonded to polystyrene (PS-OH) is used.

Then, the wafer W on which the resist pattern 402 is formed in step S3 is transferred to the hydrophobic film forming apparatus 550. In the hydrophobic film forming apparatus 550, a coating liquid is applied onto the exposed surface of the neutral layer 401 of the wafer W and the resist pattern 402 to form a hydrophobic film. Thereafter, the wafer W is transferred to the heat treatment apparatus 40, heated, and the temperature is adjusted.

Thereafter, in step S5, an organic solvent is supplied onto the wafer W, and the hydrophobic film on the resist pattern 402 is removed together with the resist pattern 402 on the wafer W as shown in FIG. Further, the upper part of the hydrophobic film on the exposed surface of the neutral layer 401 is also removed. Thus, a thin hydrophobic film 560 having a thickness of, for example, 5 nm is formed only on the exposed surface of the neutral layer 401.

Note that the other steps S1 to S3 and S6 to S9 are the same as those in the above embodiment, and the description thereof is omitted. However, since the exposed surface of the neutral layer 401 is hydrophobized in step S7, the hydrophobic polymer 406 is disposed in the middle of the hydrophobic film 560 on the hydrophobic film 560 as shown in FIG. Hydrophilic polymers 405 and 405 are disposed on both sides thereof. On the wafer W, the hydrophilic polymer 405 and the hydrophobic polymer 406 are alternately arranged in an arrangement opposite to the case where the exposed surface of the neutral layer 401 is made hydrophilic.

According to this embodiment, since the thin hydrophobic film 560 can be formed on the exposed surface of the neutral layer 401, the exposed surface can be hydrophobized. Therefore, the same effect as that of the above embodiment can be enjoyed. That is, a predetermined fine pattern of the hydrophilic polymer 405 can be appropriately formed on the wafer W, and the processing target film can be appropriately etched using the pattern as a mask in step S9. Further, the throughput of wafer processing in the substrate processing system 1 can be improved.

By the way, according to the present inventors, when the block copolymer 404 is applied on the flat neutral layer 401 in which the exposed surface exposed from the resist pattern 402 is hydrophilized or hydrophobized by surface treatment as described above. It was confirmed that the lamellar structure may not be phase-separated in a desired pattern. Specifically, the desired lamellar structure is, for example, along the longitudinal direction of the hydrophilic region 403 formed by surface-treating the neutral layer 401 as shown in FIG. However, when the block copolymer 404 is applied onto the flat neutral layer 401 and phase-separated into a lamellar structure, the lamellar structure is arranged perpendicular to the longitudinal direction of the hydrophilic region 403, for example, as shown in FIG. May end up. In addition, in FIG. 20, drawing is abbreviate | omitted about the pattern by the block copolymer 404 in the neutral layer 401 which is not surface-treated.

This is because the hydrophilic region 403 has a width orthogonal to the longitudinal direction of the hydrophilic region 403 because the hydrophilic polymer 405 and the hydrophobic polymer 406 are alternately arranged in odd layers, for example, three layers. The reason is that the polymers 405 and 406 can be stretched. Therefore, the present inventors set the width of the space portion 402b of the resist pattern 402 to either one of the hydrophilic polymer 405 or the hydrophobic polymer 406 so that the lamella structure is not arranged perpendicular to the longitudinal direction of the hydrophilic region 403. The idea was to have one layer and less than two layers. However, the width of the space portion 402b is sufficiently fine for patterning with a resist even when the hydrophilic polymer 405 and the hydrophobic polymer 406 are alternately arranged in three layers. Cannot be formed of a resist.

Therefore, the present inventors considered that the width of the space portion 402b can be increased by heating the resist pattern 402 and increasing the width of the line portion 402a of the resist pattern 402 by so-called reflow. A specific method will be described below.

When the width of the line portion 402a of the resist pattern 402 is increased by reflow, the wafer W on which the resist pattern 402 is formed after the development and post-baking in step S3 is transferred to the heat treatment apparatus 40. In the heat treatment apparatus 40, heating is performed at a temperature not lower than the glass transition point temperature of the resist and not higher than the heat resistant temperature of the resist for a predetermined time, for example, 160 ° C. for one minute. In this case, the heat treatment apparatus 40 functions as a reflow apparatus. Then, the wafer W is heated by the heat treatment apparatus 40 at a temperature equal to or higher than the glass transition temperature, and reflow occurs. For example, as shown by a broken line in FIG. As shown by a solid line in FIG. 21, the lower portion is deformed into a substantially inverted U shape with its sides extending laterally. At this time, by appropriately setting the above-described heating conditions, the spread of the line portion 402a is controlled, and the space portion 402b has a desired width, that is, either a hydrophilic polymer 405 after phase separation into a lamellar structure or a hydrophobic polymer 406 The width is adjusted to one or more layers and less than two layers. In addition, as shown in FIG. 21, the line part 402a has a substantially uniform width across the longitudinal direction.

FIG. 22A is a planar image of the resist pattern 402 when the wafer W is heated at 140 ° C. below the glass transition temperature of the resist, and FIG. 22B shows the temperature above the glass transition temperature of the resist. It is the image after heating the wafer W at 160 degreeC below the heat-resistant temperature of a resist, and making it reflow. In FIG. 22A, reflow does not occur because the heating temperature is equal to or lower than the glass transition temperature of the resist. However, in FIG. 22B, the width of the line portion 402a in plan view is widened by reflow, and the width of the space portion 402b. Can be confirmed.

The wafer W in which the width of the space portion 402b is adjusted by reflow is transferred to the ultraviolet irradiation device 41 in step S4, and is exposed to the neutral layer 401 of the exposed space portion 402b exposed from the resist pattern 402 as shown in FIG. Ultraviolet rays are irradiated. As a result, a hydrophilic region 403 corresponding to one layer of the polymers 405 and 406 after phase separation is formed in the neutral layer 401.

Thereafter, the resist pattern 402 is removed in step S5, and the block copolymer 404 is applied in step S6. Next, in step S7, the block copolymer 404 is phase-separated into a hydrophilic polymer 405 and a hydrophobic polymer 406. At this time, as shown in FIG. 24, the hydrophilic region 403 has a width corresponding to one layer of the hydrophilic polymer 405. Therefore, the hydrophilic polymer 405 is surely disposed in the hydrophilic region 403, and both sides thereof are arranged. Hydrophobic polymers 406 and 406 are disposed on the surface. And the hydrophilic polymer 405 and the hydrophobic polymer 406 are alternately arrange | positioned also on the other area | region of the neutral layer 401. FIG.

The other steps S1 to S2 and S8 to S9 are the same as those in the above embodiment, and the description thereof is omitted.

According to the present embodiment, by expanding the width of the line portion 402a by reflow, the width of the space portion 402b is, for example, one or more of the hydrophilic polymer 405 and the hydrophobic polymer 406 and less than two layers. It was adjusted. Therefore, when the block copolymer 404 is applied on the flat neutral layer 401 and phase-separated into a lamellar structure, the lamellar structure can be prevented from being arranged perpendicular to the longitudinal direction of the hydrophilic region 403. Therefore, in the present embodiment, the lamella structure can be reliably arranged along the longitudinal direction of the hydrophilic region 403.

In the above embodiment, reflow is performed by heating with the heat treatment apparatus 40. However, a heat treatment apparatus dedicated to reflow may be separately provided in the coating and developing treatment apparatus 2. Further, in the above embodiment, after the post-baking in step S3, the reflow is performed by separately heating with the heat treatment apparatus 40. However, the reflow may be performed simultaneously by adjusting the heating time and the heating temperature in the post-baking. In addition to heating the wafer W, reflow may be performed by exposing the wafer W to a solvent atmosphere of the resist to dissolve the resist.

In performing reflow, it is preferable to use a negative resist having a high heat-resistant temperature and capable of easily adjusting the width of the line portion 402a by reflow. In addition, the expansion of the width of the line portion 402 a due to reflow varies depending on the type of film serving as the base of the resist pattern 402. Therefore, the heating temperature and heating time for reflow are not limited to the above embodiment, and are appropriately set depending on the type of resist and its base film.

In the above embodiment, the case where the neutral layer 401 is hydrophilized by ultraviolet irradiation has been described as an example. However, as a matter of course, the case where the hydrophilic film 510 is formed on the exposed surface of the neutral layer 401, Even in the case of forming 560, the width of the space portion 402b may be narrowed by reflow. Even in such a case, taking the case where the hydrophilic film 510 is formed as an example, as shown in FIG. 25, for example, the neutral layer 401 and the resist pattern 402 exposed in the space 402b narrowed to the width of one layer by reflow. A coating solution is applied on top of it to form a hydrophilic film 510. Thereafter, by removing the resist pattern 402 in step S5, the hydrophilic film 510 is removed together with the resist pattern 402, and the hydrophilic film 510 is formed only in the space portion 402b whose width is narrowed by reflow.

The other steps S1 to S3 and S6 to S9 are the same as in the above embodiment.

Also in this embodiment, the hydrophilic film 510 having a width corresponding to one layer of the polymers 405 and 406 can be formed on the exposed surface of the neutral layer 401. Therefore, the same effect as when the hydrophilic region 403 is formed by ultraviolet irradiation can be obtained. That is, it is possible to prevent the lamellar structure from being arranged perpendicular to the longitudinal direction of the hydrophilic film 510.

In the above embodiment, the block copolymer 404 on the wafer W is phase-separated into a hydrophilic polymer 405 having a lamellar structure and a hydrophobic polymer 406. However, in the wafer processing method of the present invention, the block copolymer 404 is made into a cylinder. The present invention can also be applied to the case of phase separation into a hydrophilic polymer 405 and a hydrophobic polymer 406 having a structure.

In the block copolymer 404 used in this embodiment, the ratio of the molecular weight of the hydrophilic polymer 405 is 20% to 40%, and the ratio of the molecular weight of the hydrophobic polymer 406 in the block copolymer 404 is 80% to 60%. %. In the present embodiment, the substrate processing system 1 having the same structure as that of the above embodiment is used.

In this case, in step S3, a resist pattern having a circular space portion 402c in plan view is formed on the wafer W as shown in FIG. The space portions 402c are arranged in a staggered manner in a plan view.

Thereafter, when the block copolymer 404 is phase-separated in step S7, it is phase-separated into a hydrophilic polymer 405 having a cylindrical structure and a hydrophobic polymer 406 as shown in FIG. The hydrophilic polymer 405 is formed on the hydrophilic space portion 402c and on the resist pattern 402 between the two space portions 402c and 402c. The hydrophobic polymer 406 is formed on the other resist pattern 402. Then, in subsequent step S9, when the hydrophilic polymer 405 is used as a mask to etch the film to be processed on the wafer W, a predetermined hole-shaped pattern is formed on the film to be processed.

Note that the other steps S1, S2, S4 to S6, and S8 are the same as those in the above embodiment, and thus the description thereof is omitted.

According to this embodiment, the block copolymer 404 can be appropriately phase-separated into the hydrophilic polymer 405 and the hydrophobic polymer 406 having a cylindrical structure, and the etching process of the film to be processed can be appropriately performed.

The block copolymer 404 of the above embodiment has polymethyl methacrylate (PMMA) and polystyrene (PS), but includes a hydrophilic polymer having hydrophilicity and a hydrophobic polymer having hydrophobicity. It is not limited to this. For example, silicone rubber (PDMS) may be used for the hydrophilic polymer.

In the above embodiment, the neutralization or hydrophobization of the neutral layer 401 in step S4 has been performed by the coating and developing treatment apparatus 2 of the substrate processing system 1. However, the neutralization or hydrophobization of the neutral layer 401 is performed. The etching may be performed by etching apparatuses 202 to 205 of the etching processing apparatus 3, for example, an RIE apparatus.

In the above embodiment, the film to be processed on the wafer W is etched in step S9, but the wafer processing method of the present invention can also be applied when etching the wafer W itself.

The preferred embodiments of the present invention have been described above with reference to the accompanying drawings, but the present invention is not limited to such examples. It is obvious for those skilled in the art that various modifications or modifications can be conceived within the scope of the idea described in the claims, and these naturally belong to the technical scope of the present invention. It is understood. The present invention is not limited to this example and can take various forms. The present invention can also be applied to a case where the substrate is another substrate such as an FPD (flat panel display) other than a wafer or a mask reticle for a photomask.

The present invention is useful when a substrate is treated with a block copolymer containing, for example, a hydrophilic polymer having hydrophilicity and a hydrophobic polymer having hydrophobicity.

DESCRIPTION OF SYMBOLS 1 Substrate processing system 2 Coating development processing apparatus 3 Etching processing apparatus 30 Developing apparatus 31 Cleaning apparatus 32 Antireflection film forming apparatus 33 Neutral layer forming apparatus 34 Resist coating apparatus 35 Block copolymer coating apparatus 40 Heat treatment apparatus 41 Ultraviolet irradiation apparatus 202 205 Etching apparatus 300 Control unit 400 Antireflection film 401 Neutral layer 402 Resist pattern 402a Line part 402b, 402c Space part 403 Hydrophilic region 404 Block copolymer 405 Hydrophilic polymer 406 Hydrophobic polymer 500 Hydrophilic film forming apparatus 510 Hydrophilic Film 550 Hydrophobic film forming apparatus 560 Hydrophobic film W wafer

Claims (29)

1. A method of treating a substrate using a block copolymer comprising a first polymer and a second polymer,
   A neutral layer forming step of forming on the substrate a neutral layer having an intermediate affinity for the first polymer and the second polymer;
   A neutral layer treatment step of surface-treating the exposed surface of the neutral layer exposed from the resist pattern with respect to the substrate on which the resist pattern is formed on the neutral layer;
   A block copolymer coating step for coating the block copolymer on the neutral layer on the substrate from which the resist pattern has been removed after the neutral layer treatment step;
   A polymer separation step of phase-separating the block copolymer on the neutral layer into the first polymer and the second polymer;
   Have
2. The substrate processing method according to claim 1,
   The surface treatment in the neutral layer treatment step is either a hydrophobic treatment or a hydrophilization treatment of the exposed surface of the neutral layer.
3. The substrate processing method according to claim 2,
   The resist pattern formed on the neutral layer has a line width expanded by reflow.
4. The substrate processing method according to claim 3,
   The space portion of the resist pattern has a width of one or more of the first polymer or the second polymer that is phase-separated in the polymer separation step and less than two layers.
5. The substrate processing method according to claim 2,
   In the surface treatment of the neutral layer treatment step, the exposed surface of the neutral layer is irradiated with ultraviolet rays to make the exposed surface hydrophilic.
6. The substrate processing method according to claim 5,
   The wavelength of the ultraviolet light is 172 nm.
7. The substrate processing method according to claim 2,
   In the neutral layer treatment step, a hydrophilic film having hydrophilicity is formed on the exposed surface of the neutral layer and the resist pattern, and the exposed surface is hydrophilized.
   On the substrate processed in the block copolymer coating step, the hydrophilic film on the resist pattern is removed together with the resist pattern, and the hydrophilic film remains only on the exposed surface of the neutral layer.
8. The substrate processing method according to claim 2,
   In the neutral layer treatment step, a hydrophobic film having hydrophobicity is formed on the exposed surface of the neutral layer and the resist pattern, and the exposed surface is hydrophobized,
   On the substrate processed in the block copolymer coating step, the hydrophobic film on the resist pattern is removed together with the resist pattern, and the hydrophobic film remains only on the exposed surface of the neutral layer.
9. The substrate processing method according to claim 1,
   A polymer removal step of selectively removing either the first polymer or the second polymer from the phase-separated block copolymer is provided.
10. The substrate processing method according to claim 1,
    The resist pattern is a pattern having a linear line portion and a linear space portion in plan view,
    The molecular weight ratio of the first polymer in the block copolymer is 40% to 60%.
11. The substrate processing method according to claim 10,
    In the polymer separation step, the first polymer and the second polymer are alternately phase-separated into odd layers in the space portion.
12. The substrate processing method according to claim 1,
    The resist pattern is a pattern having a circular space portion in plan view,
    The molecular weight ratio of the first polymer in the block copolymer is 20% to 40%.
13. The substrate processing method according to claim 1,
    The first polymer is a hydrophilic polymer having hydrophilicity, and the second polymer is a hydrophobic polymer having hydrophobicity.
14. The substrate processing method according to claim 13,
    The hydrophilic polymer is polymethyl methacrylate;
    The hydrophobic polymer is polystyrene.
15. On a computer of a controller that controls the substrate processing system in order to cause the substrate processing system to execute the substrate processing method for processing the substrate using the block copolymer including the first polymer and the second polymer. A readable computer storage medium storing a program operating in
    The substrate processing method includes:
    A neutral layer forming step of forming on the substrate a neutral layer having an intermediate affinity for the first polymer and the second polymer;
    A neutral layer treatment step of surface-treating the exposed surface of the neutral layer exposed from the resist pattern with respect to the substrate on which the resist pattern is formed on the neutral layer
    A block copolymer coating step for coating the block copolymer on the neutral layer on the substrate from which the resist pattern has been removed after the neutral layer treatment step;
    A polymer separation step of phase-separating the block copolymer on the neutral layer into the first polymer and the second polymer;
    Have
16. A system for processing a substrate using a block copolymer comprising a first polymer and a second polymer,
    A neutral layer forming apparatus for forming on the substrate a neutral layer having an intermediate affinity for the first polymer and the second polymer;
    A neutral layer processing apparatus for surface-treating an exposed surface of the neutral layer exposed from the resist pattern with respect to a substrate having a resist pattern formed on the neutral layer;
    A block copolymer coating device for coating the block copolymer on the neutral layer on the substrate from which the resist pattern has been removed after the exposed surface is surface-treated by the neutral layer processing device;
    A polymer separator for phase-separating the block copolymer on the neutral layer into the first polymer and the second polymer;
    Have
17. The substrate processing system according to claim 16, wherein
    The surface treatment in the neutral layer treatment apparatus is either a hydrophobic treatment or a hydrophilic treatment of the exposed surface of the neutral layer.
18. The substrate processing system according to claim 17, wherein
    A reflow apparatus for widening a line width of the resist pattern formed on the neutral layer by reflow;
19. The space portion of the resist pattern after reflowing by the substrate processing system according to claim 18,
    The first polymer or the second polymer that is phase-separated by the polymer separator has a width of one or more layers and less than two layers.
20. The substrate processing system according to claim 17, wherein
    In the surface treatment of the neutral layer processing apparatus, the exposed surface of the neutral layer is irradiated with ultraviolet rays to make the exposed surface hydrophilic.
21. The substrate processing system according to claim 20, wherein
    The wavelength of the ultraviolet light is 172 nm.
22. The substrate processing system according to claim 17, wherein
    The neutral layer processing apparatus forms a hydrophilic film having hydrophilicity on the exposed surface of the neutral layer and the resist pattern, and hydrophilizes the exposed surface,
    On the substrate processed in the block copolymer coating apparatus, the hydrophilic film on the resist pattern is removed together with the resist pattern, and the hydrophilic film remains only on the exposed surface of the neutral layer.
23. The substrate processing system according to claim 17, wherein
    The neutral layer processing apparatus forms a hydrophobic film having hydrophobicity on the exposed surface of the neutral layer and the resist pattern, and hydrophobizes the exposed surface,
    On the substrate to be processed in the block copolymer coating apparatus, the hydrophobic film on the resist pattern is removed together with the resist pattern, and the hydrophobic film remains only on the exposed surface of the neutral layer.
24. The substrate processing system according to claim 17, wherein
    A polymer removing device for selectively removing either the first polymer or the second polymer from the phase-separated block copolymer is provided.
25. The substrate processing system according to claim 16, wherein
    The resist pattern is a pattern having a linear line portion and a linear space portion in plan view,
    The molecular weight ratio of the first polymer in the block copolymer is 40% to 60%.
26. The substrate processing system according to claim 25, wherein
    The polymer separator alternately phase-separates the first polymer and the second polymer into odd layers in the space portion.
27. The substrate processing system according to claim 16, wherein
    The resist pattern is a pattern having a circular space portion in plan view,
    The molecular weight ratio of the first polymer in the block copolymer is 20% to 40%.
28. The substrate processing system according to claim 16, wherein
    The first polymer is a hydrophilic polymer having hydrophilicity, and the second polymer is a hydrophobic polymer having hydrophobicity.
29. 29. The substrate processing system according to claim 28, wherein the hydrophilic polymer is polymethyl methacrylate and the hydrophobic polymer is polystyrene.

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