TW201503230A - Substrate processing method and computer storage medium - Google Patents

Abstract

According to the present invention, a guide pattern having a linear line portion and a space portion is formed on a coating film on a substrate; after that a block copolymer containing a first polymer having a polarity and a second polymer having no polarity is applied over the substrate, while respectively adjusting the film thickness and the molecular weight ratio of the first polymer in the block copolymer within predetermined ranges; then the block copolymer is subjected to phase separation into the first polymer and the second polymer; and the first polymer is selectively removed from the phase-separated block copolymer.

Description

Substrate processing method, program and computer memory medium

The present invention relates to a substrate processing method and program using a block copolymer comprising a hydrophilic (polar) hydrophilic (polar) polymer and a hydrophobic (non-polar) hydrophobic (non-polar) polymer. And computer memory media.

For example, in a manufacturing process of a semiconductor element, photolithography is performed to form a predetermined photoresist pattern on a wafer, and the photolithography process is sequentially performed, for example, on a semiconductor wafer (hereinafter referred to as "wafer"). A photoresist coating process for applying a photoresist to form a photoresist film, an exposure process for exposing a predetermined pattern to the photoresist film, a development process for developing a developed photoresist film, and the like. Then, the photoresist pattern is subjected to an etching process of the film to be processed on the wafer as a mask, and then a photoresist film removal process or the like is performed, and a predetermined pattern is formed on the film to be processed.

However, in recent years, in order to further increase the integration of semiconductor elements, it is required to refine the pattern of the film to be processed. For this reason, the photoresist pattern is miniaturized, for example, the light subjected to the exposure processing in the photolithography process is shortened. However, there is technology in the short-wavelength of the exposure light source. The limitation on the cost and the cost is to make the light shorter in wavelength, and it is still difficult to form, for example, a fine photoresist pattern of a few nanometers.

Here, a wafer processing method using a block copolymer composed of two types of block chains (polymers) of hydrophilicity and hydrophobicity has been proposed (Patent Document 1). In this method, first, a neutral layer having an intermediate affinity is formed on two types of polymers on a wafer. Further, on the neutral layer, a so-called guide pattern of lines and spaces is formed by, for example, a photoresist. Then, the block copolymer is applied to the neutral layer to separate the block copolymer into two types of hydrophilic and hydrophobic polymers to form a layered structure. Then, a fine pattern is formed on the wafer by another polymer in such a manner that any one of the polymers is selectively removed by, for example, etching or the like. Further, the pattern of the polymer is used as a mask, and the film to be processed is etched to form a predetermined pattern on the film to be processed.

[Previous Technical Literature] [Non-patent literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2008-36491

However, in one of the wafer processes using the layered structure as described above, there is a narrowing, for example, formed by a linear photoresist pattern. The problem of the width of the groove. Specifically, as shown in FIG. 22, a photoresist pattern 601 is formed on the wafer W on which the neutral layer 600 is formed, and a block copolymer is applied to the spacer portion of the photoresist pattern 601 to separate Hydrophilic polymer 602 and hydrophobic polymer 603. Further, as shown in FIG. 23, by selectively removing, for example, the hydrophilic polymer 602, a groove 610 having a width narrower than that of the spacer pattern 601 is formed.

Then, in the formation of the layered structure as shown in FIG. 22 as appropriate, the width of the spacer portion of the photoresist pattern 601 must be such that the hydrophilic polymer 602 and the hydrophobic polymer 603 are alternately arranged with odd-numbered layers. To form it. Further, when the width of the spacer portion of the photoresist pattern 601 is present, the hydrophilic polymer 602 and the hydrophobic polymer 603 cannot be disposed in an odd number of layers due to some errors, and the layered structure cannot be properly formed. Therefore, it has been desired to develop a method of stably narrowing the width of a groove even if the width of the spacer is varied.

The present invention has been made in view of the above, in the case of using a substrate comprising a block copolymer comprising a hydrophilic polymer and a hydrophobic polymer, even if the width of the spacer portion of the guide pattern is stable, the width is narrowed. The width of the groove is for the purpose.

In order to achieve the above object, the present invention is a method for treating a substrate by using a block copolymer comprising a first polymer having a polarity and a second polymer having no polarity, and characterized in that: a guide pattern forming process is performed on the substrate Forming a coating film thereon, and the coating film is formed to have a straight shape in a plan view a guiding pattern of a linear line portion and a linear spacer portion; a block copolymer coating process, applying the block copolymer to a substrate on which the guiding pattern is formed; and a polymer separation process to make the block The copolymer phase is separated into the first polymer and the second polymer; and the polymer removal process, the first polymer is selectively removed from the phase-separated block copolymer, and the block copolymer is coated. The film thickness of the block copolymer coated by the process, (1) when the exposed surface exposed from the space between the guide patterns has a polarity, the first polymer and the second polymer after phase separation 1 to 1.5 times the pattern pitch (2) when the exposed surface exposed from the space between the guide patterns has no polarity, the first polymer and the second polymer after phase separation The ratio of the molecular weight of the first polymer of the block copolymer is from 20 to 40%.

According to the present invention, the film thickness of the block copolymer applied to the substrate changes depending on whether or not the exposed surface has polarity. Further, the ratio of the molecular weight of the first polymer of the block copolymer is set to 20% to 40%. Thereby, the phase-separated semi-cylindrical first polymer can be arranged in parallel on the substrate on the upper surface of the second polymer, or the columnar first polymer can be arranged in parallel on the substrate in the second polymer. At this time, the first polymer is automatically arranged at the center of the spacer even if the width of the spacer portion of the guide pattern due to, for example, a photoresist pattern changes. Further, by selectively removing the first polymer, for example, the upper surface of the second polymer can be formed in a state of being recessed in the downward direction. As a result, for example, the second polymer is etched, whereby the depressed portion of the second polymer is removed first. borrow Therefore, the guide pattern due to, for example, the photoresist pattern is not affected by the variation in the width of the spacer, and the fine groove can be formed by the second polymer.

When the exposed surface exposed from the interval portion of the guiding pattern is not polar and the film thickness of the block copolymer coated in the block copolymer coating process is 1 times the pattern pitch, or is guided from the above The exposed surface of the pattern is exposed to have a polarity, and when the film thickness of the block copolymer applied in the block copolymer coating process is 1.5 times the pattern pitch, the polymer removal process may be used in the polymer removal process. The substrate on which the first polymer and the second polymer are phase-separated is irradiated with an energy ray, and then the predetermined polymer is supplied to the substrate to dissolve and remove the first polymer.

The first polymer is in the second polymer, and is arranged in a columnar or semi-cylindrical shape parallel to the upper surface of the substrate and parallel to the line portion of the guiding pattern, and the width of the spacer portion may be larger than the cylindrical shape. The diameter of the aforementioned first polymer in the shape of a semi-cylindrical shape.

The exposed surface exposed from the partition portion of the guiding pattern has a polarity, and the exposed surface may be either an antimony oxide film or an antireflection film formed on the underside of the coating film.

The first polymer may be polymethylmethacrylate, and the second polymer may be polystyrene.

Further, according to another aspect of the invention, there is provided a program for operating on a computer that controls a control unit of the substrate processing system in order to execute the substrate processing method by a substrate processing system.

Further, according to another aspect of the present invention, a readable computer memory medium storing the aforementioned program is provided.

According to the present invention, in the substrate treatment using the block copolymer comprising the hydrophilic polymer and the hydrophobic polymer, even if the width of the partition portion of the guide pattern fluctuates, the groove width can be stabilized and narrowed.

1‧‧‧Substrate processing system

30‧‧‧Developing device

31‧‧‧cleaning device

32‧‧‧Reflex prevention film forming device

33‧‧‧Neutral layer forming device

34‧‧‧Photoresist coating device

35‧‧‧ block copolymer coating device

40‧‧‧ Heat treatment unit

156‧‧‧block copolymer supply unit

190‧‧‧ Mixer

300‧‧‧Control Department

400‧‧‧1st polymer

401‧‧‧2nd polymer

410‧‧‧Anti-reflection film

411‧‧‧resist pattern

412‧‧‧ block copolymer

W‧‧‧ wafer

W ₀ ‧‧‧ coated surface

Fig. 1 is a plan view showing the outline of a configuration of a substrate processing system of the present embodiment.

Fig. 2 is a side view showing the outline of the configuration of the substrate processing system of the embodiment.

Fig. 3 is a side view showing the outline of the configuration of the substrate processing system of the embodiment.

Fig. 4 is an explanatory view showing a longitudinal section of a case where a block copolymer coated on a wafer is phase-separated into a first polymer and a second polymer.

Fig. 5 is an explanatory view showing a longitudinal section of a case where a block copolymer coated on a wafer is phase-separated into a first polymer and a second polymer.

Fig. 6 is an explanatory view showing a longitudinal section of a case where a block copolymer coated on a wafer is phase-separated into a first polymer and a second polymer.

[Fig. 7] A longitudinal section showing a case where the first polymer is selectively removed Illustration of the diagram.

Fig. 8 is an explanatory view showing a longitudinal section of a case where a second polymer is subjected to a predetermined thickness etching.

Fig. 9 is an explanatory view showing a longitudinal section of a case where a block copolymer coated on a wafer is phase-separated into a first polymer and a second polymer.

Fig. 10 is an explanatory view showing a longitudinal section of a case where a block copolymer coated on a wafer is phase-separated into a first polymer and a second polymer.

FIG. 11 is an explanatory view showing a longitudinal section of a case where a block copolymer coated on a wafer is phase-separated into a first polymer and a second polymer.

Fig. 12 is an explanatory view showing a longitudinal section of a case where a second polymer is subjected to a predetermined thickness etching.

[Fig. 13] A flow chart illustrating the main process of wafer processing.

Fig. 14 is an explanatory view showing a longitudinal section of a case where an anti-reflection film is formed on a wafer.

Fig. 15 is an explanatory view showing a longitudinal section of a state in which a photoresist pattern is formed on an antireflection film.

Fig. 16 is an explanatory view showing a longitudinal section of a case where a block copolymer is applied to a spacer of a photoresist pattern.

Fig. 17 is an explanatory view showing a longitudinal section of a case where a block copolymer is phase-separated into a first polymer and a second polymer.

Fig. 18 is an explanatory view showing a plane in which a block copolymer phase is separated into a first polymer and a second polymer.

Fig. 19 is an explanatory view showing a longitudinal section of a case where a first polymer is selectively removed.

Fig. 20 is an explanatory view showing a longitudinal section of a case where a second polymer is subjected to a predetermined thickness etching.

FIG. 21 is an explanatory view showing a longitudinal section of a pattern formed by the first polymer and the second polymer when the film thickness of the block copolymer is increased.

FIG. 22 is an explanatory view showing a longitudinal section of a case where a block copolymer is phase-separated into a hydrophilic polymer and a hydrophobic polymer in a conventional wafer processing.

FIG. 23 is an explanatory view showing a longitudinal section of a case where a pattern of a hydrophobic polymer is formed on a wafer in a conventional wafer process.

Hereinafter, embodiments of the present invention will be described. FIG. 1 is an explanatory view showing a schematic configuration of a substrate processing system 1 for performing substrate processing in the present embodiment. 2 and 3 are schematic side views showing the internal structure of the substrate processing system 1.

As shown in FIG. 1, the substrate processing system 1 has an integrated structure, and includes a cassette station 10 in which a cassette C for accommodating a plurality of wafers W is carried in and out, and a processing station 11 having a wafer W. A plurality of various processing devices that are subjected to predetermined processing; and the interface station 13 performs the reception of the wafer W between the exposure device 12 adjacent to the processing station 11.

A cassette mounting table 20 is provided in the cassette station 10. In the cassette mounting table 20, for example, four cassette mounting plates 21 on which the cassette C is placed when the cassette C is loaded and unloaded outside the substrate processing system 1 are provided.

In the cassette station 10, as shown in FIG. 1, a wafer transfer device 23 that is freely movable on a transport path 22 extending in the X direction is provided. The wafer transfer device 23 can also move freely in the vertical direction and around the vertical axis (theta direction), and can be used in the cassette C on each of the cassette mounting plates 21 and the third block G3 of the processing station 11 to be described later. The wafer W is transferred between the receiving devices.

A plurality of, for example, four blocks G1, G2, G3, and G4 including various devices are provided in the processing station 11. For example, the first block G1 is provided on the front side of the processing station 11 (the negative side in the X direction of FIG. 1), and the second block is provided on the back side of the processing station 11 (the positive side in the X direction of FIG. 1). Block G2. Further, the third block G3 is provided on the card station 10 side of the processing station 11 (the negative side in the Y direction of FIG. 1), and is provided on the interface station 13 side of the processing station 11 (the positive direction side in the Y direction of FIG. 1). There is block 4 G4.

For example, in the first block G1, as shown in FIG. 2, a plurality of liquid processing apparatuses such as the developing device 30, the cleaning device 31, the anti-reflection film forming device 32, and the photoresist coating device 34 are laminated in this order. a block copolymer coating device 35 for performing a development process on the wafer W, wherein the cleaning device 31 applies an organic solvent to the wafer W and washes the wafer W, and the reflection is prevented. The film forming apparatus 32 forms an anti-reflection film on the wafer W, and the photoresist coating device 34 applies a photoresist solution on the wafer W to form a photoresist film, and the block copolymer coating device 35 is attached thereto. The block copolymer is coated on the wafer W.

For example, the developing device 30, the cleaning device 31, the anti-reflection film forming device 32, the photoresist coating device 34, and the block copolymer coating device 35 are arranged side by side in the horizontal direction. In addition, the images The number or arrangement of the device 30, the cleaning device 31, the anti-reflection film forming device 32, the neutral layer forming device 33, the photoresist coating device 34, and the block copolymer coating device 35 can be arbitrarily selected.

In the developing device 30, the cleaning device 31, the anti-reflection film forming device 32, the photoresist coating device 34, and the block copolymer coating device 35, for example, a predetermined coating liquid is applied onto the wafer W. Rotating coating. In the spin coating, for example, a coating liquid is discharged from the coating nozzle onto the wafer W, and the wafer W is rotated to spread the coating liquid onto the surface of the wafer W.

Further, the block copolymer applied to the wafer W by the block copolymer coating device 35 has a first polymer and a second polymer. As the first polymer, a hydrophilic polymer which is a polymer having polarity (hydrophilic) is used, and as the second polymer, a hydrophobic polymer which is a polymer which is not polar (hydrophobic) is used. In the present embodiment, for example, polymethyl methacrylate (PMMA) is used as the hydrophilic (polar) polymer, and polystyrene (PS) is used as the hydrophobic (non-polar) polymer. Further, the ratio of the molecular weight of the hydrophilic polymer of the block copolymer is 20% to 40%, preferably 12 to 30%. Further, the ratio of the molecular weight of the hydrophobic polymer of the block copolymer is 80% to 60%, preferably 88% to 70%. Further, the block copolymer is a polymer in which a hydrophilic polymer and a hydrophobic polymer are linearly bonded.

In the second block G2, for example, as shown in FIG. 3, heat treatment devices 40 are arranged in the vertical direction and horizontal direction to perform heat treatment of the wafer W, and the polymer separation device 41 is coated with the block copolymer. The block copolymer coated on the wafer W by the device 35 is phase-separated into a hydrophilic polymer and a hydrophobic polymer; the adhesive device 42 is used to hydrophobize the wafer W; the peripheral exposure device 43 is applied to the wafer W. The outer peripheral portion is exposed; and the ultraviolet irradiation device 44 irradiates the wafer W with ultraviolet rays. The heat treatment apparatus 40 includes a hot plate on which the wafer W is placed and heated, and a cooling plate for mounting and cooling the wafer W, and a cooling plate. Further, the polymer separation device 41 is also a device for applying heat treatment to the wafer W, and its configuration is the same as that of the heat treatment device 40. Further, the number or arrangement of the heat treatment device 40, the polymer separation device 41, the adhesion device 42, the peripheral exposure device 43, and the ultraviolet irradiation device 44 can be arbitrarily selected.

For example, in the third block G3, a plurality of receiving devices 50, 51, 52, 53, 54, 55, 56 are sequentially provided from the bottom. Further, in the fourth block G4, a plurality of receiving devices 60, 61, and 62 are sequentially provided from the bottom.

As shown in FIG. 1, a wafer transfer region D is formed in a region surrounding the first block G1 to the fourth block G4. In the wafer transfer region D, a plurality of wafer transfer devices 70 having, for example, transfer arms that are freely movable in the Y direction, the X direction, the θ direction, and the up and down direction are disposed. The wafer transfer device 70 is movable in the wafer transfer region D, and transports the wafer W to the surrounding first block G1, second block G2, third block G3, and fourth block G4. Scheduled device.

Further, in the wafer transfer region D, a shuttle transport device that linearly transports the wafer W between the third block G3 and the fourth block G4 is provided. Set to 80.

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

As shown in FIG. 1, the wafer transfer apparatus 100 is provided in the positive direction side of the X direction of the 3rd block G3. The wafer transfer apparatus 100 has, for example, a transfer arm that is freely movable in the X direction, the θ direction, and the vertical direction. The wafer transfer apparatus 100 moves up and down while supporting the wafer W, and can transport the wafer W to each of the receiving apparatuses in the third block G3.

The interface station 13 is provided with a wafer transfer device 110 and a transfer device 111. The wafer transfer device 110 has, for example, a transfer arm that is freely movable in the Y direction, the θ direction, and the vertical direction. In the wafer transfer apparatus 110, for example, the wafer W is supported by the transfer arm, and the wafer W can be transferred between each of the transfer device, the transfer device 111, and the exposure device 12 in the fourth block G4.

In the above substrate processing system 1, a control unit 300 is provided as shown in FIG. The control unit 300 is, for example, a computer, and has a program storage unit (not shown). A program for controlling the processing of the wafer W of the substrate processing system 1 is stored in the program storage unit. Further, in the program storage unit, a program for controlling the operation of the drive system such as the various processing devices or the transfer device described above and realizing the peeling process described later in the substrate processing system 1 is also stored. In addition, the aforementioned programs are recorded on a computer such as a hard disk (HD), a floppy disk (FD), a compact disk (CD), a magneto-optical disk (MO), a memory card, etc. The read memory media may be installed in the control unit 300 by the memory medium.

Next, a description will be given of the principle of wafer processing in the present embodiment, when the wafer processing performed by the substrate processing system 1 configured as described above is used.

In the block copolymer having the first polymer (having polarity) and the second polymer (having no polarity), for example, the ratio of the molecular weight of the first polymer is 20% to 40%, and the second polymer is used. When the ratio of the molecular weight is 80% to 60%, the pattern obtained by separating the block copolymer into the first polymer and the second polymer is arranged in a columnar shape in the second polymer. . Further, the columnar pattern by the first polymer after the phase separation differs from the direction of the arrangement depending on the state of the coated surface on the wafer W on which the block copolymer is applied.

The coated surface to which the block copolymer is applied is, for example, a cylindrical pattern obtained by the first polymer after phase separation when the energy difference between the first polymer and the second polymer is equal. The second polymer is vertically aligned on the coated surface. Further, when the first polymer is vertically aligned on the coated surface, generally, the first polymer and the second polymer have the same energy difference, that is, two types of pairs are formed on the wafer. The polymer has a neutral layer of intermediate affinity. Further, the neutral layer was used as a coated surface of the coated block copolymer.

On the other hand, when the block copolymer is applied to a coated surface having a small difference in energy from any of the first polymer or the second polymer, the first polymer after phase separation or The second polymer is arranged in parallel on the coated surface. Specifically, when the block copolymer is applied to, for example, a non-polar surface, for example, as shown in FIG. 4, the first polymer 400 (polymer having polarity) and the second polymer 401 after phase separation are separated. The difference in energy between the non-polar coating surface and the non-polar coating surface is increased, so that it is not arranged to be in contact with the coated surface W _{0 of the} wafer W. In other words, the second polymer 401 is arranged in contact with the coated surface W ₀ , and the first polymer 400 is arranged in a columnar shape in the second polymer 401 . At this time, the first polymer 400 is parallel to the coated surface W _{0 of the} wafer W. Further, the intervals between the columnar first polymers 400 are also formed to be equal. This is because the energy difference at the interface between the first polymer 400 and the second polymer 401 is equal to the entire pattern, and the first polymer 400 and the second polymer 401 are autonomously moved. Further, in FIG. 4, the first 400-based polymer in the second polymer 401 are arranged parallel to the pitch of the cylindrical pattern when the wafer W is set to L _0, it is applied to the coated surface in W _When the film thickness of the block copolymer of ₀ is L ₀ , a pattern like this is formed.

Next, a case where the film thickness of the block copolymer applied to the wafer W is set to L ₀ /2 which is a half of the pattern pitch L ₀ will be described. When the film thickness of the block copolymer is L ₀ /2 and then the block copolymer is phase-separated, for example, as shown in FIG. 5, the coating surface W ₀ of the wafer W is layered. 2 polymer 401, and the first polymer 400 is layered on the second polymer 401. However, in general, the first polymer 400 has a smaller energy difference from the second polymer 401 than the energy difference in the atmosphere. Therefore, the first polymer 400 is formed into a semicircular shape in cross section as shown in FIG. 6 so as to minimize the contact area with the atmosphere.

When the first polymer 400 is selectively removed, as shown in FIG. 7, the upper surface of the second polymer 401 is formed into a shape that is recessed in a downward direction in a semicircular shape. In addition, when the first polymer 400 is a hydrophilic polymer (polymethyl methacrylate), for example, when the first polymer 400 is selectively removed, for example, when the wafer W is irradiated with an ultraviolet ray as an energy ray, The J chain of polymethyl methacrylate will be truncated, and for example, the second polymer 401 which is a polystyrene of a hydrophobic polymer will generate a bridging reaction. Then, when isopropyl alcohol (IPA) which is a polar organic solvent is supplied to the wafer W, the first polymer 400 which is a hydrophilic polymer in which the J chain is blocked by ultraviolet irradiation is dissolved and selectively removed. On the other hand, the second polymer 401 remains on the coated surface W ₀ of the wafer W in a state in which the upper surface thereof is recessed in a semicircular shape. Further, the wavelength of the ultraviolet ray to be irradiated is, for example, 172 nm or 222 nm.

Further, as the energy ray, for example, an electron beam can be used in addition to the ultraviolet ray.

Then, on the coated surface W ₀ , the remaining second polymer 401 is subjected to isotropic etching for a predetermined time by dry etching such as RIE (Reactive Ion Eching), and the film of the second polymer 401 is used. The thickness is reduced, and as shown in Fig. 8, the depressed portion of the second polymer 401 is removed first, and the undepressed portion remains. As a result, the groove 401a is formed by leaving only the second polymer 401 having a predetermined thickness. At this time, the film thickness of the remaining second polymer 401 is formed to be less than L ₀ /2 by etching.

Here, the inventors of the present invention thought that the interval between the semi-cylindrical first polymers 400 is also formed to have the same property, and has a line portion and a spacer portion, and the so-called line-to-gap photoresist pattern is spaced apart. The width of the portion is set to be larger than the diameter of the semi-cylindrical first polymer 400, and one semi-cylindrical first polymer 400 is disposed. In this case, since the first polymer 400 is arranged autonomously at the center of the spacer, the first polymer can be obtained even if the width of the spacer of the photoresist pattern cannot be formed to a predetermined width due to some error. 400 is arranged at the center of the spacer. Further, as shown in FIG. 8, the width of the groove of the photoresist pattern can be narrowed by removing the first polymer 400 and removing a part of the second polymer. This is an overview of the principles of the invention.

Further, in the above description, the example has been described where when the block copolymer coating on the coated surface W ₀ non-polar, polar but a coating on the coating surface W ₀ block copolymers, even lines The film thickness of the applied block copolymer is the same, and the pattern formed by the first polymer 400 and the second polymer 401 is also different. Specifically, when the coated surface W ₀ has a polarity, when the block copolymer is applied at a thickness of, for example, one half of the pattern pitch L ₀ , the first polymer 400 after phase separation is as shown in FIG. 9 . The layers are formed in a coating surface W ₀ having a small energy difference. The second polymer 401 is arranged in a layer on the upper surface of the first polymer 400. In this case, since the first polymer 400 is stable in a state of being in contact with the coated surface W ₀ , unlike the case shown in FIG. 6 , the semi-cylindrical shape is not formed at this point of time. In other words, when the coating surface W ₀ has a polarity, when the film thickness of the block copolymer is L ₀ /2, a semi-cylindrical pattern due to the first polymer 400 is not formed.

Then, when the film thickness of the applied block copolymer is the same as the pattern pitch L ₀ , as shown in FIG. 10 , the first polymer 400 is separately arranged on the coated surface W ₀ side and the atmosphere layer 2 . In the layer, the second polymer 401 is in a state of being sandwiched between the two layers of the first polymer 400. Further, as described above, the first polymer 400 arranged on the upper surface of the second polymer 401 is arranged to have a semi-cylindrical shape on the upper surface of the second polymer 401 in order to minimize the contact area with the atmosphere. shape. Therefore, when the coated surface W ₀ is a surface having a polarity, the thickness of the block copolymer applied to the coated surface W ₀ is set to be the same as the pattern pitch L ₀ , and the coated surface W ₀ has polarity. When the film thickness of the block copolymer is set to be half of the pattern pitch L ₀ , the semi-cylindrical pattern by the first polymer 400 can be arranged on the surface of the second polymer 401.

When the coating is applied and, in the above, as shown in the first polymer 400 is formed into a semi-cylindrical shape 6, i.e., although the clear coating having a face surface W ₀ is the polar The thickness of the block copolymer of the surface W ₀ is L ₀ , and when the coated surface W ₀ is a surface having no polarity, it is 1/2L ₀ . However, as shown in FIG. 4 , even if the first polymer 400 is formed as In the case of a columnar shape, as described above, the width of the groove due to the photoresist pattern can also be narrowed. When the first polymer 400 is formed in a columnar shape, when the coated surface W ₀ is a surface having a polarity, the thickness of the block copolymer is 3/2 L ₀ , and when the coated surface W ₀ is a surface having no polarity, the line L _{0 is} .

In this case, for example, as shown in FIG. 12, first, the second polymer 401 is etched by dry etching until the first polymer 400 is exposed. Then, the exposed first polymer 400 is irradiated with ultraviolet rays, and then, by supplying isopropanol, as shown in FIG. 7, it is possible to remain in the state in which the upper surface of the second polymer 401 is recessed downward. Round W. Further, although FIG. 12 are diagrams of the coated surface of the wafer W W ₀ an example where the non-polar surface, however, the coated surface even when the surface W ₀ having the polarity, except that the thickness of the block copolymer is 3 The other points except /2L _{0 are} the same as in the case of FIG.

The method of substrate processing according to the present embodiment is based on the above findings, and the wafer processing performed by the substrate processing system 1 will be described next. Figure 13 is a flow chart showing an example of the main process of wafer processing.

First, the cassette C storing a plurality of wafers W is carried into the cassette station 10 of the substrate processing system 1. By the wafer transfer device 23, the wafers W in the cassette C are sequentially transferred to the processing station. The receiving device 53 of 11.

Next, the wafer W is transferred to the heat treatment apparatus 40 by the wafer transfer apparatus 70, and temperature adjustment is performed. Then, the wafer W is transported to the anti-reflection film forming device 32 by the wafer transfer device 70, and an anti-reflection film 410 is formed on the wafer W as shown in FIG. 14 (the process S1 of FIG. 13). Thereafter, the wafer W is transported to the heat treatment apparatus 40 for heating and temperature adjustment.

Next, the wafer W is transported to the receiving device 54 by the wafer transfer device 100. Thereafter, the wafer W is transferred to the adhesive device 42 by the wafer transfer device 70, and is adhered. After the wafer The W is transported to the photoresist coating device 34 by the wafer transfer device 70, and a photoresist is applied onto the anti-reflection film 410 of the wafer W to form a photoresist 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 transported to the receiving device 55 by the wafer transfer device 70.

Next, the wafer W is transported to the peripheral exposure device 43 by the wafer transfer device 70, and peripheral exposure processing is performed. Thereafter, the wafer W is transported to the receiving device 56 by the wafer transfer device 70. Next, the wafer W is transported to the receiving device 52 by the wafer transfer device 100, and is transported to the receiving device 62 by the shuttle transport device 80.

Thereafter, the wafer W is transported to the exposure device 12 by the wafer transfer device 110 of the interface station 13, and exposure processing is performed.

Next, the wafer W is transferred from the exposure device 12 to the receiving device 60 by the wafer transfer device 110. Thereafter, the wafer W is transferred to the heat treatment apparatus 40 by the wafer transfer apparatus 70, and is baked after exposure. 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 transported to the heat treatment apparatus 40 by the wafer transfer apparatus 70, and post-baking processing is performed. As a result, as shown in FIG. 15, a predetermined photoresist pattern 411 is formed on the anti-reflection film 410 of the wafer W as a guide pattern (engineering S2 of FIG. 13). In the present embodiment, the photoresist pattern 411 has a pattern of a so-called line and gap between the line portion 411a and the spacer portion 411b. Further, the width of the partition portion 411b is set such that one columnar or semi-cylindrical first polymer 400 is disposed in the partition portion 411b. Further, the height of the photoresist pattern 411 is formed to be the same height as the pattern pitch L ₀ by the block copolymer 412 as will be described later.

Next, 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 is supplied to the wafer W, and as shown in FIG. 16, the block copolymer 412 is coated in the spacer portion 411b of the photoresist pattern 411 (FIG. 13). Engineering S3). At this time, since the thickness of the line portion 411a of the photoresist pattern 411 is L ₀ , the thickness of the block copolymer 412 applied in the spacer portion 411b is also L ₀ .

Next, the wafer W is transferred to the polymer separation device 41 by the wafer transfer device 70. In the polymer separation device 41, the wafer W is subjected to heat treatment at a predetermined temperature. As a result, as shown in FIGS. 17 and 18, the block copolymer 412 on the wafer W is phase-separated into a first polymer 400 as a hydrophilic polymer and a second polymer 401 as a hydrophobic polymer. (Project S4 of Figure 13).

Here, as described above, in the block copolymer 412, the ratio of the molecular weight of the first polymer 400 is 20% to 40%, and the ratio of the molecular weight of the second polymer 401 is 80% to 60%. Further, in the present embodiment, the coated surface W _{0 to} which the block copolymer 412 is applied, in other words, the exposed surface exposed from the partition portion 411b of the resist pattern 411 is the anti-reflection film 410, and the anti-reflection film 410 is used. A hydrophilic (having a polar) film. In the case of the process S4, as shown in FIG. 17 and FIG. 18, the first polymer 400 is arranged in a layered manner on the side of the anti-reflection film 410, and is arranged in a semi-cylindrical shape on the upper surface of the second polymer 401.

Then, the wafer W is transferred to the ultraviolet irradiation device 44 by the wafer transfer device 70, and is irradiated with ultraviolet rays (the process S5 of FIG. 13). Thereby, the first polymer 400 has a J chain which is cut off, for example, to be soluble in an organic solvent.

Next, the wafer W is transferred to the cleaning device 31 by the wafer transfer device 70 and washed with an organic solvent. Thus, when it is soluble in the organic solvent, the first polymer 400 is as shown in FIG. It is shown that it is selectively removed from the upper surface of the second polymer 401 (item S6 of Fig. 13). Further, at this time, the first polymer 400 arranged on the upper surface of the anti-reflection film 410 remains.

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

Then, the cassette C is transported to an etching processing apparatus provided outside the substrate processing system 1, and the second polymer 402 is subjected to dry etching (engineering S7 of FIG. 13). Further, at this time, the first polymer 400 interposed between the second polymer 401 and the anti-reflection film 410 is also etched in the same manner. As a result, as shown in FIG. 20, the trench 401a is formed by the second polymer 401 between the line portions 411a of the photoresist pattern 411. Then, the second polymer 401 is used as a mask, and the anti-reflection film 410 and the wafer W are etched to form a predetermined pattern on the wafer W.

According to the above embodiment, in response to the coating surface coated with a block copolymer of W ₀ 412 whether the polarity change in the thickness of the coating to produce the block copolymer of the wafer W of 412. Further, the ratio of the molecular weight of the first polymer 400 of the block copolymer 412 is set to 20% to 40%. Therefore, by separating the block copolymer 412, the semi-cylindrical first polymer 400 can be arranged on the upper surface of the second polymer in parallel and on the upper surface of the wafer W. In this case, when the width of the partition portion 411b of the guide pattern due to, for example, the photoresist pattern 411 is changed so as not to be predetermined in a layered structure, for example, the first polymer 400 may be arranged autonomously at the interval. The center of the part 411b. In addition, by selectively removing the semi-cylindrical first polymer 400, for example, the upper surface of the second polymer 401 can be formed in a state of being recessed in the downward direction. As a result, for example, the second polymer 401 is etched, whereby the recessed portion of the second polymer 401 is removed first. Thereby, for example, the center portion of the photoresist pattern 411 is not affected by the variation in the width of the spacer portion 411b, and the fine groove can be formed by the second polymer 401.

In the above embodiment, an example in which the first polymer 400 is arranged in a semi-cylindrical shape on the upper surface of the second polymer has been described. However, as described above, the first polymer 400 may be arranged in a columnar shape. The inside of the second polymer 401. However, when the first polymer 400 is formed on the upper surface of the second polymer 401 in a semi-cylindrical shape, it is not necessary to dry-etch the second polymer 401 when the first polymer 400 is selectively removed. Since the first polymer 400 is exposed, it is preferable to form the first polymer 400 in a semi-cylindrical shape on the upper surface of the second polymer 401. In other words, when the coated surface W ₀ coated with the block copolymer 412 has a polarity, the film thickness of the block copolymer 412 is set to L ₀ , and when the coated surface W _{0 is} not polar, the block copolymer 412 is used. The film thickness was set to L ₀ /2.

Further, when the film thickness of the block copolymer 412 is further increased, the second polymer 401 is sandwiched between the columnar first polymer 400, for example, as shown in FIG. A cylindrical first polymer 400. Fig. 21 is an example of a state in which the block copolymer 412 is applied and the phases are separated by a thickness of 3L ₀ /2 on the coating surface W ₀ having no polarity. At this time, the first polymer 400 has a regular triangular shape in a cross-sectional view so that the distance between the first polymers 400 is uniform. Therefore, when viewed in a plan view, since the columnar first polymer 400 and the semi-cylindrical first polymer 400 are arranged differently, the grooves of the second polymer 401 cannot be formed properly. Therefore, it is necessary to further set the film thickness of the block copolymer 412 above the columnar first polymer 400 to the film thickness of the first polymer 400 in which the semi-cylindrical shape is not arranged. Specifically, when the coated surface W ₀ coated with the block copolymer 412 has a polarity, it is necessary to set the film thickness of the block copolymer 412 to be 1 to 1.5 times the distance between the patterns L ₀ , and the coated surface W _{When 0 is} not polar, it is necessary to set the film thickness of the block copolymer 412 to 0.5 to 1 times the pitch L ₀ .

Further, in the above embodiment, the width of the spacer portion 411b of the resist pattern 411 is set to the first polymer 400 in which a semi-cylindrical or columnar shape is arranged, but the width of the spacer portion 411b is not set. It is limited to the content of this embodiment. For example, the width of the partition portion 411b may be set to two or more first polymers 400, and the width of the partition portion 411b may be arbitrarily set. In any case, one of the first polymers 400 is arranged in the partition portion 411b, and as long as the width of the partition portion 411b is larger than the diameter of the semi-cylindrical or cylindrical first polymer 400, The first polymer 400 is arranged at equal intervals in the plan view at the interval portion 411b.

In the above embodiment, the coated surface W ₀ having a polarity is the anti-reflection film 410 formed on the wafer W. However, the coated surface W ₀ having a polarity may be, for example, a tantalum oxide film. Another hydrophilic film formed on the wafer W. Further, the non-polar coated surface W ₀ may be a hydrophobic film such as a film of polystyrene formed on the wafer W. However, when the coated surface W ₀ has the same energy difference between the first polymer 400 and the second polymer 401, that is, the coated surface W ₀ is the first polymer 400 and the second polymer 401. In the case of the neutral layer having the intermediate affinity, as described above, since the first polymer 400 is vertically aligned on the coated surface W ₀ , the neutral layer cannot be used as the coated surface W _{0 of the} block copolymer.

Further, in the above embodiment, wet etching such as an organic solvent is used when the first polymer 400 is selectively removed, but the first polymer 400 may be selectively removed by dry etching.

Further, in the above embodiment, as shown in FIGS. 4 and 12, when the first polymer 400 is arranged in the second polymer 401 and arranged in a columnar shape parallel to the wafer W, the second embodiment is described. Although the polymer 401 is subjected to dry etching and the first polymer is irradiated with ultraviolet rays, the ultraviolet ray may be irradiated before the second polymer 401 is dry etched. In this case, the second polymer 401 may be dry-etched after ultraviolet irradiation, or may be supplied with isopropyl alcohol after ultraviolet irradiation, and then dry-etched. According to the present inventors, even after ultraviolet irradiation, Isopropanol is supplied before dry etching, and isopropanol is allowed to permeate into the second polymer to dissolve the first polymer 400.

The productivity of wafer processing can be improved by supplying isopropyl alcohol after ultraviolet irradiation and before dry etching. That is, since the first polymer 400 is removed by isopropyl alcohol after the dry etching is supplied, the dry etching is performed again in the step S7, and therefore, between the substrate processing system 1 and the external etching processing apparatus. The transfer of the wafer W occurs twice. In this regard, if the first polymer 400 is previously dissolved by supplying isopropyl alcohol before dry etching, the first polymer 400 is removed again after the second polymer is removed by dry etching in the etching apparatus, instead of The wafer W needs to be transferred from the etching processing apparatus to the substrate processing system 1.

Heretofore, the preferred embodiments of the present invention have been described with reference to the accompanying drawings, but the present invention is not limited to the examples. It is obvious that various modifications and alterations are conceivable within the scope of the invention as described in the appended claims. The present invention is not limited to this example, and various aspects can be employed. The present invention is also applicable to a case where the substrate is another substrate such as an FPD (flat panel display) other than a wafer or a grating for a photomask.

[Industrial availability]

The present invention employs a block copolymer comprising a hydrophilic polymer having, for example, hydrophilicity and a hydrophobic polymer having hydrophobicity, and is useful for treating a substrate.

400‧‧‧1st polymer

401‧‧‧2nd polymer

W‧‧‧ wafer

W ₀ ‧‧‧ coated surface

Claims (7)

A substrate processing method for treating a substrate by using a block copolymer comprising a first polymer having a polarity and a second polymer having no polarity, characterized in that: a guide pattern forming process is formed on the substrate a coating film in which a coating pattern having a linear line portion and a linear partition portion is formed in a plan view by a coating film; and a block copolymer coating process for coating a substrate on which the guiding pattern is formed The block copolymer; polymer separation engineering, phase separating the block copolymer into the first polymer and the second polymer; and polymer removal engineering, selectively separating the block copolymer from the phase Removing the first polymer, the film thickness of the block copolymer applied in the block copolymer coating process, and (1) when the exposed surface exposed from the space between the guide patterns has a polarity 1 to 1.5 times the pattern pitch of the first polymer and the second polymer after phase separation (2) when the exposed surface exposed from the space between the guiding patterns has no polarity, after phase separation The aforementioned first polymer and The ratio of the pattern pitch of the second polymer is 0.5 to 1 time, and the ratio of the molecular weight of the first polymer of the block copolymer is 20% to 40%. The substrate processing method of claim 1, wherein The first polymer is formed in the second polymer in a columnar or semi-cylindrical shape parallel to the upper surface of the substrate, and is arranged in parallel with the line portion of the guiding pattern, and the width of the spacer portion is larger than the aforementioned The diameter of the aforementioned first polymer in a cylindrical or semi-cylindrical shape. The substrate processing method according to claim 1 or 2, wherein the exposed surface exposed from the interval of the guiding pattern is non-polar and the block copolymer coated in the block copolymer coating process is applied When the film thickness is one time of the pattern pitch, or the exposed surface exposed from the interval portion of the guiding pattern has polarity, and the film thickness of the block copolymer applied in the block copolymer coating process is a pattern pitch At 1.5 times, in the polymer removal process, the substrate after phase separation of the first polymer and the second polymer is irradiated with an energy ray, and then the predetermined treatment liquid is supplied to the substrate to dissolve and remove the first 1 polymer. The substrate processing method according to claim 1 or 2, wherein the exposed surface exposed from the space between the guiding patterns has a polarity, and the exposed surface is formed of an oxide film or formed under the coating film. Any of the reflection preventing films. The substrate processing method according to claim 1 or 2, wherein the first polymer is polymethyl methacrylate. The second polymer is polystyrene. A program for performing a substrate processing method according to any one of claims 1 to 5 by a substrate processing system, and operating on a computer that controls a control unit of the substrate processing system. A readable computer memory medium that stores a program as claimed in item 6 of the patent application.