WO2014119444A1 - 基板処理方法及びコンピュータ記憶媒体 - Google Patents

基板処理方法及びコンピュータ記憶媒体 Download PDF

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Publication number
WO2014119444A1
WO2014119444A1 PCT/JP2014/051225 JP2014051225W WO2014119444A1 WO 2014119444 A1 WO2014119444 A1 WO 2014119444A1 JP 2014051225 W JP2014051225 W JP 2014051225W WO 2014119444 A1 WO2014119444 A1 WO 2014119444A1
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Prior art keywords
polymer
wafer
resist
substrate
pattern
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PCT/JP2014/051225
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English (en)
French (fr)
Japanese (ja)
Inventor
村松　誠
北野　高広
忠利 冨田
啓士 田内
聡一郎 岡田
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東京エレクトロン株式会社
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Priority to KR1020157019983A priority Critical patent/KR102122343B1/ko
Publication of WO2014119444A1 publication Critical patent/WO2014119444A1/ja

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/033—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers
    • H01L21/0334—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane
    • H01L21/0337—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane characterised by the process involved to create the mask, e.g. lift-off masks, sidewalls, or to modify the mask, e.g. pre-treatment, post-treatment

Definitions

  • the present invention relates to a substrate treatment using a block copolymer comprising a hydrophilic (polar) polymer having hydrophilicity (polarity) and a hydrophobic (nonpolar) polymer having hydrophobicity (no polarity).
  • the present invention relates to a substrate processing method and a computer storage medium.
  • a resist coating process for coating a resist solution on a semiconductor 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.
  • 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.
  • Non-Patent Document 1 a wafer processing method using a block copolymer composed of two types of polymers has been proposed (Non-Patent Document 1).
  • 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.
  • the neutral layer on the resist pattern is removed, and then the resist pattern itself is also removed.
  • a pattern of the neutral layer 601 is formed on the antireflection film 600 of the wafer W as shown in FIG. After that, as shown in FIG.
  • a block copolymer 610 is applied on the neutral layer 601 patterned with the antireflection film 600, and the hydrophilic polymer 611 and the hydrophobic polymer 612 are phase-separated from the block copolymer 610. To do.
  • the antireflection film 600 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.
  • the neutral layer 601 formed in a predetermined pattern on the antireflection film 600 functions as a guide for regularly arranging the hydrophilic polymer 611 and the hydrophobic polymer 612.
  • the hydrophilic polymer 611 is removed, whereby a fine pattern of the hydrophobic polymer 612 is formed on the wafer W.
  • 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.
  • the antireflection film 600 and the neutrality described above are used as a guide.
  • a hydrophobic polymer 612 and a resist can be used as a guide.
  • a hydrophobic polymer 612 and a resist can be used as a guide.
  • a hydrophobic polymer 612 and a resist can be used as a guide.
  • a hydrophobic polymer 612 and a resist can be used as a guide.
  • a hydrophobic polymer 612 and a resist can be used as an example of the process in such a case, first, a hydrophobic polymer 612 is applied on the antireflection film 600 of the wafer W, and a resist pattern is formed on the hydrophobic polymer 612. Next, the hydrophobic polymer 612 is etched using the resist pattern as a mask, and then the resist pattern is removed, thereby forming a pattern of the hydrophobic polymer 612 as shown in FIG. 20, for example.
  • the resist pattern could not be removed successfully, which might affect the subsequent pattern formation with the block copolymer.
  • the reason for this is that when the etching of the hydrophobic polymer 612 is performed by so-called dry etching, for example, by plasma processing, the resist pattern is carbonized during dry etching, which makes it difficult to remove the resist pattern. It is done.
  • the resist pattern In order to remove the resist pattern, it may be possible to use a strong organic solvent or to perform dry ashing. Such a technique cannot be used because it changes.
  • the resist pattern can be formed of a resist film that is not easily carbonized during dry etching, but in that case, a special resist solution is required, and versatility is significantly reduced.
  • the present invention has been made in view of such points, and in the substrate processing using a block copolymer containing a hydrophilic polymer and a hydrophobic polymer, the guide is appropriately formed on the substrate, thereby making the hydrophilic property.
  • the object is to arrange the polymer and the hydrophobic polymer in a desired pattern.
  • the present invention provides a method for treating a substrate using a block copolymer containing a first polymer and a second polymer, wherein a coating film soluble in an alkaline solution is formed.
  • a resist pattern is formed with a resist film on a coating film soluble in an alkaline solution, a predetermined pattern is formed on the substrate using the resist pattern as a mask, and then the coating film is removed with the alkaline solution.
  • the hydrophilic polymer and the hydrophobic polymer can be arranged in a desired pattern.
  • 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.
  • the hydrophilic polymer and the hydrophobic polymer are formed in a desired pattern by appropriately forming the guide on the substrate. Can be arranged.
  • FIG. 1 is an explanatory diagram showing an outline of a configuration of a substrate processing system 1 according to the present embodiment.
  • 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.
  • the coating and developing treatment apparatus 2 includes a cassette station 10 in which a cassette C containing a plurality of wafers W is loaded and unloaded, and a treatment station having a plurality of various treatment apparatuses for performing predetermined processing on the wafers W. 11 and an interface station 13 for transferring the wafer W between the exposure station 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, for example, four cassette mounting plates 21 on which the cassette C is mounted when the cassette C is carried in and out of the coating and developing treatment apparatus 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 ( ⁇ 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.
  • 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.
  • 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.
  • a plurality of liquid processing apparatuses for example, a developing apparatus 30 that develops the wafer W, an alkaline solution supply apparatus 31 that supplies an alkaline solution onto the wafer W, and a wafer W
  • An antireflection film forming device 32 for forming an antireflection film on the wafer a neutral layer forming device 33 for forming a neutral layer by applying a neutral agent on the wafer W, and a resist film by applying a resist solution on the wafer W
  • the resist coating device 34 for forming the block copolymer and the block copolymer coating device 35 for coating the block copolymer on the wafer W are stacked in order from the bottom.
  • TMAH tetramethylammonium hydroxide
  • the developing device 30, the alkaline solution supply 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 alkaline solution supply 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.
  • the alkali solution supply 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 predetermined coating solution is applied onto the wafer W.
  • a predetermined coating solution is applied onto the wafer W.
  • Spin coating is performed.
  • 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.
  • the block copolymer applied onto the wafer W by the block copolymer coating device 35 includes a first polymer and a second polymer.
  • a hydrophilic polymer having hydrophilicity (polarity) is used
  • a hydrophobic polymer having hydrophobicity (polarity) is used.
  • PMMA polymethyl methacrylate
  • PS polystyrene
  • 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.
  • 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.
  • a random copolymer or an alternating copolymer of polymethyl methacrylate and polystyrene is used as the neutral layer.
  • neutral means having an intermediate affinity for the hydrophilic polymer and the hydrophobic polymer.
  • a heat treatment apparatus 40 for performing heat treatment of the wafer W for performing heat treatment of the wafer W, an adhesion apparatus 41 for hydrophobizing the wafer W, and a peripheral exposure apparatus 42 for exposing the outer peripheral portion of the wafer W are vertically arranged. Are arranged side by side in the horizontal direction.
  • 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.
  • 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 adhesion apparatus 41, and the peripheral exposure apparatus 42 can be arbitrarily selected.
  • 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.
  • a wafer transfer region D is formed in a region surrounded by the first block G1 to the fourth block G4.
  • a wafer transfer region D for example, a plurality of wafer transfer devices 70 having transfer arms that are movable in the Y direction, the X direction, the ⁇ direction, and the vertical direction are arranged.
  • 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.
  • 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.
  • 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 ⁇ 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 ⁇ 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.
  • 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.
  • 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.
  • a wafer transfer mechanism 215 for transferring the wafer W is provided in the transfer chamber 214.
  • 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.
  • 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 a film to be processed such as a hydrophilic polymer or an antireflection film is performed by a reactive gas (etching gas), ions, or radicals.
  • etching gas reactive gas
  • 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.
  • HD computer-readable hard disk
  • FD flexible disk
  • CD compact disk
  • MO magnetic optical desk
  • FIG. 6 is a flowchart showing an example of main steps of such wafer processing.
  • 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.
  • 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 neutral layer forming device 33 by the wafer transfer device 70, and the neutral layer 400 is formed on the entire surface of the wafer W as shown in FIG. 7 (step S1 in FIG. 6). Although not shown, the surface of the wafer W before forming the neutral layer 400 is covered with a silicon oxide film, and the surface of the wafer W is hydrophilic. Thereafter, the wafer W is transferred to the heat treatment apparatus 40, heated, temperature-controlled, and then returned to the delivery apparatus 53.
  • the wafer W is transferred to the resist coating unit 34 by the wafer transfer unit 70, and a resist solution is applied onto the neutral layer 400 of the wafer W, and the first resist is applied to the entire surface of the wafer W as shown in FIG. A film 401 is formed (step S2 in FIG. 6).
  • a resist solution is applied onto the neutral layer 400 of the wafer W, and the first resist is applied to the entire surface of the wafer W as shown in FIG.
  • a film 401 is formed (step S2 in FIG. 6).
  • an ArF resist is used as the resist solution in the present embodiment.
  • the wafer W is transferred to the heat treatment apparatus 40 by the wafer transfer apparatus 70.
  • the first resist film 401 is heated at a temperature higher than the heat resistant temperature, in other words, at a temperature higher than the temperature at which the first resist film 401 is deprotected (step S3 in FIG. 6).
  • the first resist film 401 which is an ArF resist, is deprotected over the entire surface of the wafer W.
  • the heated first resist film 401 becomes a coating film soluble in tetramethylammonium hydroxide (TMAH) which is an alkaline solution.
  • TMAH tetramethylammonium hydroxide
  • the ArF resist is deprotected at 200 ° C. or higher. Therefore, when the wafer W on which the first resist film 401 is formed is heated by the heat treatment apparatus 40.
  • the temperature is 200 ° C. or higher.
  • the heat resistance temperature of the neutral layer 400 formed in the lower layer of the first resist film 401 is about 240 ° C.
  • the heating temperature of the wafer W when the first resist film 401 is deprotected needs to be equal to or higher than the heat resistance temperature of the first resist film 401 and lower than the heat resistance temperature of the neutral layer 400. Therefore, when the first resist film 401 is an ArF resist, for example, the heating temperature of the wafer W is 200 ° C. or higher and lower than 240 ° C., more preferably 210 ° C. to 230 ° C.
  • the wafer W is transferred to the antireflection film forming apparatus 32 by the wafer transfer apparatus 70, and as shown in FIG. 8, an antireflection film 402 is formed on the first resist film 401 deprotected by the heat treatment. (Step S4 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 delivery device 54 by the wafer transfer device 100. Thereafter, the wafer W is transferred to the adhesion device 41 by the wafer transfer device 70 and subjected to an adhesion process.
  • the wafer W is transferred again to the resist coating device 34 by the wafer transfer device 70.
  • a resist solution is applied onto the antireflection film 402 of the wafer W to form a second resist film 403 as shown in FIG.
  • the wafer W is transferred to the heat treatment apparatus 40 by the wafer transfer apparatus 70 and pre-baked.
  • the heating temperature in the pre-baking process is different from the heating process of the first resist film 401 in that the temperature is lower than the heat resistant temperature of the ArF resist so that the second resist film 403 is not deprotected.
  • the wafer W is transferred to the delivery device 55 by the wafer transfer device 70.
  • the wafer W is transferred to the peripheral exposure device 42 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.
  • 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 is formed by the second resist film 403 as shown in FIG. 9 (step S5 in FIG. 6).
  • the resist pattern formed by the second resist film 403 is a so-called line-and-space resist pattern having a linear line portion 403a and a linear space portion 403b in plan view.
  • the width of the space portion 403b is set so that a hydrophilic polymer and a hydrophobic polymer are alternately arranged in odd-numbered layers in the space portion 403b as described later.
  • 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.
  • the cassette C containing the wafer W is unloaded from the coating / development processing apparatus 2, and then the etching processing apparatus 3. It is carried 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.
  • the inside of the load lock device 213a is sealed and decompressed.
  • the inside of the load lock device 213a and the inside of the transfer chamber chamber 214 evacuated to a predetermined degree of vacuum are communicated.
  • 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.
  • the wafer W is etched using the resist pattern of the second resist film 403 as a mask, and the antireflection film 402 is first etched as shown in FIG. 10 (step S6 in FIG. 6).
  • the wafer W is transferred to the etching apparatus 204 by the wafer transfer mechanism 215.
  • the etching apparatus 204 the first resist film 401 and the neutral layer 400 on the wafer W are continuously etched as shown in FIG. 11 using the resist pattern of the second resist film 403 and the pattern of the antireflection film 402 as a mask. (Step S7 in FIG. 6).
  • 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 wafer W is unloaded from the etching processing apparatus 3 and loaded into the coating and developing processing apparatus 2 again.
  • the wafer W carried into the coating and developing treatment apparatus 2 is carried into the alkaline solution supply apparatus 31 by the wafer transfer apparatus 70.
  • the alkaline solution supply device 31 the alkaline solution is supplied onto the wafer W, and the first resist film 401 that has been deprotected by the heat treatment and becomes soluble in the alkaline solution is removed from the wafer W.
  • the antireflection film 402 and the second resist film 403 are removed from the wafer W as shown in FIG. 12 together with the first resist film 401 (step S8 in FIG. 6).
  • step S8 in FIG. 6 only the pattern of the neutral layer 400 remains on the wafer W.
  • the second resist film 403 is etched at the same time when the first resist film 401 and the neutral layer 400 are etched by the etching apparatus 204, so that depending on the thickness of the second resist film 403, In some cases, the film is completely removed at the stage of the etching process. However, since the antireflection film 402 functions as a mask even after the second resist film 403 is removed, the thickness of the second resist film 403 is medium. Any setting can be used as long as the conductive layer 400 is appropriately etched.
  • the wafer W is transferred to the block copolymer coating device 35.
  • the block copolymer coating device 35 the block copolymer 404 is coated on the pattern of the neutral layer 400 on the wafer W as shown in FIG. 13 (step S9 in FIG. 6).
  • the wafer W is transferred by the wafer transfer apparatus 70 to a heat treatment apparatus 40 as a polymer separation apparatus.
  • a heat treatment at a predetermined temperature is performed on the wafer W.
  • the block copolymer 404 on the wafer W is phase-separated into the hydrophilic polymer 405 and the hydrophobic polymer 406 as shown in FIGS. 14 and 15 (step S10 in FIG. 6).
  • the molecular weight ratio of the hydrophilic polymer 405 is 40% to 60%
  • the molecular weight ratio of the hydrophobic polymer 406 is 60% to 40%.
  • the hydrophilic polymer 405 and the hydrophobic polymer 406 are alternately arranged in an odd number of layers, for example, three layers.
  • the hydrophobic polymer 406 is disposed in the middle of the neutral layer 400 and the neutral layer 400, and the hydrophilic polymers 405 and 405 are disposed on both sides thereof.
  • the hydrophilic polymer 405 and the hydrophobic polymer 406 are alternately arranged on other regions of the neutral layer 400.
  • 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.
  • the cassette C containing the wafer W is unloaded from the coating / developing apparatus 2 and loaded again into the etching apparatus 3.
  • the wafer W taken out from the cassette C is transferred to the etching apparatus 202.
  • the hydrophilic polymer 405 is selectively removed by the etching process as shown in FIG. 16, and a predetermined pattern of the hydrophobic polymer 406 is formed (step S11 in FIG. 6).
  • the wafer W is transferred to the etching apparatus 204 by the wafer transfer mechanism 215.
  • the film to be processed on the wafer W is etched using the hydrophobic polymer 406 on the wafer W as a mask.
  • the hydrophobic polymer 406 and the antireflection film are removed, and a predetermined pattern is formed on the film to be processed.
  • the wafer W is stored in the cassette C, and the cassette C storing the wafer W is unloaded from the etching processing apparatus 3 to complete a series of wafer processing.
  • the first resist film 401 applied in step S2 is deprotected by heat treatment in step S3 to form a coating film soluble in an alkaline solution. Then, a resist pattern is formed by the second resist film 403 on the coating film soluble in the alkaline solution, and a predetermined pattern is formed on the wafer W using the resist pattern as a mask.
  • the second resist film 403 is removed. Therefore, the second resist film 403 can be easily removed without using a strong organic solvent or a special resist solution, and a guide for arranging the hydrophilic polymer 405 and the hydrophobic polymer 406 on the wafer W is provided. It can be formed appropriately. As a result, the hydrophilic polymer 405 and the hydrophobic polymer 406 can be arranged in a desired pattern.
  • a method of forming an antireflection film 402 on the lower surface of the neutral layer 400 is generally used, and for example, a pattern of the neutral layer 400 is formed on the wafer W. After that, it is necessary to separately remove the antireflection film 402.
  • the deprotection first resist film 401 formed on the upper surface of the neutral layer 400 that is, an alkali is used.
  • the antireflection film 402 can be easily removed together with the first resist film 401 with an alkaline solution. Therefore, when forming a predetermined pattern on the wafer W using the block copolymer 404, the process can be simplified.
  • the first resist film 401 is formed of an ArF resist
  • the alkaline solution can be obtained by deprotection.
  • a soluble resist such as a KrF resist can be used, and the present invention is not limited to this embodiment.
  • the first resist film 401 and the second resist film 403 are both formed of ArF resist.
  • the first resist film 401 and the second resist film 403 are formed of different resists. May be.
  • the physical property of being soluble in an alkaline solution does not change even from the heat treatment during the formation of the neutral layer 400 to the heat treatment in the process of forming a resist pattern by the second resist film 403. Any selection is possible.
  • tetramethylammonium hydroxide is used as an alkaline solution for removing the deprotected first resist film 401.
  • an alkaline solution may be used.
  • the present embodiment is not limited to this embodiment and can be arbitrarily selected.
  • isopropyl alcohol (IPA) to tetramethylammonium hydroxide may be used. By adding isopropyl alcohol, the first resist film 401 can be more reliably removed in step S8.
  • the neutral layer 400 is formed on the lower surface of the first resist film 401 as a base film having a guide function for arranging the hydrophilic polymer 405 and the hydrophobic polymer 406.
  • the base film functioning as the guide is not limited to the neutral layer 400 and can be arbitrarily set.
  • another base film for example, polystyrene or the like can be used.
  • the base film functioning as a guide is not always necessary.
  • the first resist film 401 is directly formed on the upper surface of the wafer W, and the wafer W itself is etched in step S7 to form a pattern on the wafer W. Also good. In such a case, the wafer W itself is used as a guide, or, for example, as shown in FIG. 17, the neutral layer 400 is formed in the recess of the etched wafer W to make the wafer W flat, and the neutral layer 400 and the wafer A guide may be formed by W.
  • the developing device 30 and the alkaline solution supply device 31 are separate devices.
  • the alkaline solution supply device 31 is used.
  • the first resist film 401 in step S8 may be removed in the developing device 30 by omitting it.
  • the thickness of the first resist film 401 is preferably 20 nm to 100 nm, more preferably 40 nm to 60 nm.
  • 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.
  • FPD flat panel display
  • 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.

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PCT/JP2014/051225 2013-01-30 2014-01-22 基板処理方法及びコンピュータ記憶媒体 WO2014119444A1 (ja)

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Citations (4)

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Publication number Priority date Publication date Assignee Title
JP2008036491A (ja) * 2006-08-03 2008-02-21 Nippon Telegr & Teleph Corp <Ntt> パターン形成方法及びモールド
WO2012014700A1 (ja) * 2010-07-28 2012-02-02 株式会社 東芝 パターン形成方法及びポリマーアロイ下地材料
JP2012061531A (ja) * 2010-09-14 2012-03-29 Tokyo Ohka Kogyo Co Ltd ブロックコポリマーを含む層のパターン形成方法
WO2012046770A1 (ja) * 2010-10-07 2012-04-12 東京応化工業株式会社 ガイドパターン形成用ネガ型現像用レジスト組成物、ガイドパターン形成方法、ブロックコポリマーを含む層のパターン形成方法

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JPS62136028A (ja) * 1985-12-10 1987-06-19 Matsushita Electric Ind Co Ltd 有機膜のパタ−ン形成方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008036491A (ja) * 2006-08-03 2008-02-21 Nippon Telegr & Teleph Corp <Ntt> パターン形成方法及びモールド
WO2012014700A1 (ja) * 2010-07-28 2012-02-02 株式会社 東芝 パターン形成方法及びポリマーアロイ下地材料
JP2012061531A (ja) * 2010-09-14 2012-03-29 Tokyo Ohka Kogyo Co Ltd ブロックコポリマーを含む層のパターン形成方法
WO2012046770A1 (ja) * 2010-10-07 2012-04-12 東京応化工業株式会社 ガイドパターン形成用ネガ型現像用レジスト組成物、ガイドパターン形成方法、ブロックコポリマーを含む層のパターン形成方法

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