TW201519320A - Pattern forming method and heating device - Google Patents

Abstract

An object of the invention is to encourage phase separation by promoting the fluidization of polymers of a block copolymer. This object is achieved by a pattern formation method that includes a step of forming a film of a block copolymer containing at least two polymers on a substrate, a step of subjecting the block copolymer to phase separation by heating the film of the block copolymer in a solvent vapor atmosphere, and a step of removing one of the polymers from the phase-separated block copolymer film.

Description

Pattern forming method and heating device

The present invention relates to a self-assembled (DSA) lithography technique, and more particularly to a pattern forming method and a heating apparatus using the same.

The use of a self-assembled lithography technique in which a block copolymer is disposed in a self-assembled manner has been studied (for example, Patent Documents 1, 2 and Non-Patent Document 1). In the self-assembled lithography technique, first, for example, a solution containing a block copolymer of an A polymer chain and a B polymer chain is applied to a substrate to form a film produced by the block copolymer. Next, when the substrate is heated, the A polymer chain which is randomly dissolved in the film and the B polymer chain are phase-separated to form a regularly disposed A polymer region and B polymer region.

The phase separation of the block copolymer is carried out by heating the A polymer and the B polymer to cause the A polymers to aggregate with each other, and the B polymers are aggregated with each other.

[Practical Technical Literature]

[Patent Literature]

[Patent Document 1]: JP-A-2005-29779

[Patent Document 2]: JP-A-2007-125699

[Non-patent literature]

[Non-Patent Document 1]: KW Guarini, et al., "Optimization of Diblock Copolymer Thin Film Self Assembly", Advanced Materials, 2002, 14, No. 18, September 16, pp. 1290-1294. (p. 1290, Ll.31-51)

When the substrate on which the film of the block copolymer is formed is heated to separate the block copolymer to form the A polymer region and the B polymer region, generally, the higher the heating temperature, the longer the heating time, and the more reliably Phase separation. However, when the heating temperature is too high, the solvent of the A polymer and the B polymer evaporates to make it difficult to fluidize each, and the A polymer and/or the B polymer evaporate. Further, if the heating time is increased, problems such as a decrease in the amount of manufacturing process are likely to occur.

In view of the above problems, the present invention provides a pattern forming method and a heating apparatus which can promote phase separation by promoting fluidization of a polymer of a block copolymer.

According to a first aspect of the present invention, there is provided a pattern forming method comprising the steps of: forming a film of a block copolymer containing at least two polymers on a substrate; and forming a film of the block copolymer in a solvent vapor. a step of heating the substrate to phase separate the block copolymer; and a step of removing one of the films of the phase-separated block copolymer.

According to a second aspect of the present invention, there is provided a heating apparatus comprising: a mounting table; a substrate disposed in a container and having a film on which a block copolymer is formed; and a heating unit built in the mounting table to be placed The substrate on the mounting table is heated; a solvent vapor supply unit supplies a gas containing solvent vapor in the container; and an exhaust unit that exhausts the gas in the container.

According to an embodiment of the present invention, there is provided a pattern forming method and a heating apparatus which can promote phase separation by promoting fluidization of a polymer of a block copolymer.

10‧‧‧ heating device

202‧‧‧Container body

202S‧‧‧ Sealing member

203‧‧‧ cover

204‧‧‧ Wafer Mounting Table

204h‧‧‧heating department

204P‧‧‧Power supply

21‧‧‧ film

220‧‧‧Processing room

221‧‧‧ frame

222‧‧‧ bottom

231‧‧‧Edge

232‧‧‧Upper wall

233‧‧‧ gas supply road

234‧‧‧Rectifier board

234S‧‧‧slit

235‧‧‧heater

241‧‧‧lifting pin

242‧‧‧ Lifting mechanism

243‧‧‧ Coverage

261‧‧‧Pipe

270‧‧‧ solvent vapor supply mechanism

271‧‧‧Solvent tank

272‧‧‧Flow Controller

273‧‧‧ gasifier

274‧‧‧Pipe

275‧‧‧Injector

276‧‧‧Replenishment slot

281‧‧‧Exhaust road

282‧‧‧The Department of Cavity

283‧‧‧Exhaust pipe

300‧‧‧Control Department

DM‧‧‧PMMA polymer area

DS‧‧‧PS polymer area

F‧‧‧heating device

HP‧‧‧ heating plate

L‧‧‧Light source

OS‧‧‧Organic solvent

W‧‧‧ wafer

1(a) to 1(e) are explanatory views for explaining a pattern forming method which is produced in an embodiment of the present invention.

2(a) to (c) are surface images of a pattern formed by a pattern forming method according to an embodiment of the present invention.

Fig. 3 is a schematic view showing the configuration of a heating device produced in an embodiment of the present invention.

[Best Mode for Carrying Out the Invention]

Hereinafter, embodiments that do not limit the exemplary embodiments of the present invention will be described with reference to the accompanying drawings. In the drawings, the same or corresponding reference numerals are given to the same or corresponding components, and the repeated description is omitted.

Fig. 1 shows a partial cross-section of each step of a substrate (e.g., a semiconductor wafer) processed by a pattern forming method according to an embodiment of the present invention.

First, a polystyrene (PS)-polymethyl methacrylate (PMMA) block copolymer is coated on a semiconductor wafer (hereinafter simply referred to as a wafer) W as a substrate by, for example, a spin coating method ( Hereinafter, a solution in which PS-b-PMMA is dissolved in an organic solvent (hereinafter also referred to as a coating liquid) is used to form a film 21 of PS-b-PMMA as shown in Fig. 1(a). In this film 21, the PS polymer and the PMMA polymer are randomly mixed with each other.

Next, as shown in FIG. 1(b), the wafer W on which the film 21 of PS-b-PMMA is formed is carried into the heating device F, and placed on the heating plate HP. By heating the wafer W at a predetermined temperature in a solvent vapor environment by the heating plate HP, phase separation occurs in the PS-b-PMMA in the film 21 on the wafer W. The PS polymer region DS is alternately disposed with the PMMA polymer region DM by phase separation. Further, in order to arrange the PS polymer region DS of the PS-b-PMMA and the PMMA polymer region DM in a predetermined pattern, it is preferable to form a guide pattern on the surface of the wafer W.

Here, as a solvent, if it is a soluble PS polymer and a PMMA polymer, it is no special. Further, for example, toluene, acetone, ethanol, methanol, cyclohexanone or the like can be used. Further, for example, by spraying a solvent using a sprayer, a spray of the solvent is supplied to the heat device F as an inert gas, and a solvent vapor environment can be generated in the heating device F.

Further, the temperature of the film 21 in heating is preferably higher than the glass transition temperature of PS-b-PMMA, for example, a temperature ranging from about 150 ° C to about 350 ° C.

After a predetermined period of time, the supply of the solvent vapor in the heating device F is stopped, and in order to dry the film 21, the PS-b-PMMA is used in a gas atmosphere of an inert gas (a rare gas such as nitrogen, argon or helium). The film 21 is further heated. Thereby, the solvent (and the solvent) in the film 21 is evaporated. Further, the temperature of the film 21 at the time of drying is preferably lower than the glass transition temperature so that the PS polymer and the PMMA polymer do not flow during drying.

After the completion of the heating, as shown in FIG. 1(c), the film 21 of the PS-b-PMMA on the wafer W is a rare gas such as argon (Ar) or helium (He), or a gas atmosphere of an inert gas such as nitrogen. Under ultraviolet light. The ultraviolet light is not particularly limited as long as it has a wavelength component belonging to the ultraviolet region, but preferably has a wavelength component of, for example, 200 nm or less. Further, the ultraviolet rays preferably contain a wavelength component of 185 nm or less which can be absorbed by PMMA. When ultraviolet rays having a wavelength component of a wavelength of 200 nm or less are used, as the light source L, a Xe excimer lamp that emits ultraviolet rays having a wavelength of 172 nm can be suitably used.

When it is considered that the film 21 of the PS-b-PMMA is irradiated with ultraviolet rays, the crosslinking reaction occurs in the PS, so that PS becomes difficult to dissolve in the organic solvent, and on the other hand, since the main chain is cut in the PMMA, the PMMA becomes easy. The organic solvent is dissolved. Further, in the case of using ultraviolet rays having a wavelength of 172 nm, the irradiation intensity (dose) is preferably about 180 mJ or less. When the film 21 of the PS-b-PMMA is irradiated with ultraviolet rays having a wavelength of 172 nm at a dose larger than 180 mJ, the organic solvent is easily immersed in the polymer region DS by the organic solvent when the film 21 of the PS-b-PMMA is supplied to the organic solvent. As a result, the PS polymer region DS swells and becomes difficult to remove the PMMA polymer region DM. Further, when the dose of ultraviolet rays is larger than 180 mJ, the PMMA polymer region DM has a problem of deterioration and solidification, and there is a fear that it is difficult to dissolve in an organic solvent.

Further, although the oxygen concentration in the gas atmosphere around the wafer W is lowered by the inert gas, it is sufficient that the oxygen concentration in the inert gas atmosphere is, for example, 400 ppm or less.

Next, as shown in FIG. 1(d), the organic solvent OS is supplied to the film 21 of the PS-b-PMMA. The PMMA polymer region DM in the film 21 is dissolved by the organic solvent OS to leave the PS polymer region DS on the surface of the wafer W. Here, as the organic solvent OS, for example, isopropyl alcohol (IPA) can be suitably used.

After the predetermined time has elapsed, the surface of the wafer W is dried, and as shown in FIG. 1(e), a pattern generated by the PS polymer region DS is obtained on the surface of the wafer W.

According to the pattern forming method produced in the above embodiment, since the heating of the film 21 of the PS-b-PMMA is performed in a solvent vapor atmosphere, the film 21 during heating can absorb the solvent. Therefore, even if the solvent remaining in the film 21 evaporates during heating, the concentration of the PS polymer and the PMMA polymer (for the solvent and the solvent) in the film 21 is suppressed by the absorbed solvent. Therefore, maintaining the fluidity of the PS polymer and the PMMA polymer can simplify phase separation. Thus, phase separation can be promoted by promoting the fluidization of PS-b-PMMA.

Further, for example, when the film 21 is heated in an atmospheric environment, the solvent remaining in the film 21 is evaporated, and the fluidity of the PS polymer and the PMMA polymer is lost. Therefore, the heating temperature has to be, for example, about 150 ° C. Below the level. In this low temperature, phase separation takes time and the amount of processing is reduced. On the other hand, according to the pattern forming method of the present embodiment, the film 21 is heated in a solvent vapor atmosphere, so that the heating temperature can be increased. Thereby, phase separation can be further promoted.

Then, the result of forming the pattern generated by the PS polymer region DS formed in accordance with the above-described pattern forming method will be described with reference to FIG.

2(a) and 2(b) are scanning electron microscope (SEM) images of the top surface of the pattern formed using PS-b-PMMA. Specifically, the top surface of the pattern composed of the PS polymer region DS shown in Fig. 1(e) is displayed. Further, when these patterns are formed, the guide pattern is not used, so that it is a fingerprint-like pattern.

Further, in the pattern shown in Fig. 2(a), when the film 21 of the PS-b-PMMA is heated (Fig. 1(b)), the gas atmosphere around the wafer W is a toluene vapor atmosphere. The partial pressure of toluene at this time was about 15 Torr (this partial pressure of toluene plus nitrogen gas became normal pressure). Further, in the pattern shown in Fig. 2(b), when the film 21 of the PS-b-PMMA is heated, the gas atmosphere around the wafer W is made into a toluene vapor atmosphere. The partial pressure of toluene at this time was about 30 Torr. Further, in FIG. 2(c), for comparison, a pattern (PS polymer region DS) formed by heating the wafer W at atmospheric pressure in air is displayed. Comparing these SEM images, it is found that the wafer W (and the film 21) is heated in a gas atmosphere of toluene vapor, and the time is short, and a clearer pattern can be obtained. In the opinion of the present invention, the fluidity of the PS polymer and the PMMA polymer in the membrane 21 of the PS-b-PMMA is improved by the toluene vapor as compared with the case of the air alone.

Next, a heating apparatus according to an embodiment of the present invention will be described with respect to a pattern forming method suitable for carrying out the embodiment of the present invention. Fig. 3 is a schematic configuration diagram of a heating device.

Referring to Fig. 3, the heating device 10 includes a cylindrical container body 202 having an upper end opening and a bottom portion, and a lid body 203 covering the upper end opening of the container body 202. The container body 202 includes a frame body 221 having an annular shape, a bottom portion 222 having a meandering shape extending from the bottom of the frame body 221, and a wafer mounting table 204 supported by the bottom portion 222. A heating unit 204h is provided inside the wafer mounting table 204, and the heating unit 204h is connected to the power source 204P. Thereby, the wafer W placed on the wafer stage 204 is heated. The wafer mounting table 204 is heated by the heating unit 204h, the power source 204P, and a temperature controller (not shown) to heat the wafer W placed on the wafer mounting table 204.

The wafer mounting table 204 is provided with a plurality of lift pins 241 for transmitting the wafer W to and from an external transport mechanism (not shown), and the lift pins 241 are arbitrarily movable up and down by the lift mechanism 242. . Reference numeral 243 in the figure is a cover that is disposed on the back surface of the wafer stage 204 and surrounds the periphery of the elevating mechanism 242. The container body 202 and the lid body 203 are configured to be arbitrarily movable up and down relative to each other. In this example, the lid body 203 can be attached to the container body 202 at the processing position and the upper side of the container body 202 by a lifting mechanism (not shown). The substrate can be lifted and lowered at any position.

On the other hand, in the lid body 203, the edge portion 231 of the lid body 203 is placed on the top surface of the casing 221 of the container body 202 via a sealing member 202S such as an O-ring. Thereby, the upper end opening of the container body 202 is closed by the lid body 203. The processing chamber 220 is partitioned between the container body 202 and the lid 203.

The gas supply path 233 is penetrated in the central portion of the lid body 203, and the gas supply path 233 is for supplying a solvent vapor-containing gas to the wafer W placed on the wafer mounting table 204 (hereinafter referred to as solvent vapor alone). A pipe 261 connected to a solvent vapor supply mechanism 270 to be described later is connected to the gas supply path 233. Further, a nitrogen supply source (not shown) of the rinse processing chamber 220 is connected to the pipe 261, and nitrogen gas as a flushing gas can be supplied to the processing chamber 220.

A rectifying plate 234 is disposed below the lower end portion of the gas supply path 233. A plurality of slits (or openings) 234S are formed in the rectifying plate 234. The plurality of slits 234S allow the solvent vapor flowing out from the gas supply path 233 to flow toward the wafer stage 204, and the space above the rectifying plate 234 (on the side of the gas supply path 233) and the lower side (on the wafer stage 204 side) The space is created in a way that creates a huge pressure difference. Therefore, the solvent vapor supplied to the processing chamber 220 through the gas supply path 233 spreads in the lateral direction (toward the outer periphery of the lid 203) on the upper side of the rectifying plate 234, and flows toward the wafer W through the slit 234S. Therefore, the solvent W can be supplied to the wafer W at a nearly uniform concentration.

Further, a flat hollow portion 282 having an annular planar shape is formed inside the upper wall portion 232 of the lid body 203, and the hollow portion 282 is planarly extended in a region other than the central region where the gas supply path 233 is formed. . The hollow portion 282 is connected to the exhaust passage 281 which extends in the vertical direction on the outer circumferential side of the lid body 203, that is, on the outer side of the wafer W on the wafer mounting table 204, and is opened in the processing chamber 220. . Further, in the cavity portion 282, for example, a plurality of (for example, six) exhaust pipes 283 are connected in the vicinity of the center of the lid body 203. The exhaust pipe 283 is connected to the injector 275, and the injector 275 is connected to the complementary groove 276.

In addition, reference numeral 235 in FIG. 3 denotes a heater by which a cover body is attached by a heater 235 203 heats the predetermined temperature. Thereby, the condensation of the solvent vapor to the lid body 203 is suppressed.

The solvent vapor supply mechanism 270 has a solvent tank 271, a flow rate controller 272, and a vaporizer 273. The solvent is stored in the inside of the solvent tank 271, and the inside is pressurized with nitrogen gas from a nitrogen supply source (not shown), whereby the solvent flows out to the pipe 274, and the flow rate controller 272 performs flow rate control to supply the gasifier 273. . The vaporizer 273 sprays the solvent and supplies it to the pipe 261 through the pipe 274 together with the nitrogen gas supplied from the nitrogen gas supply source.

Further, in the heating device 10, as shown in FIG. 3, the control unit 300 is provided, and the control unit 300 constitutes a heating device as shown by a one-dot chain line in the figure, and the power source 204P, the solvent vapor supply mechanism 270, the injector 275, and the like. 10 parts or components are electrically connected. The control unit 300 is constituted by, for example, a computer, and has a program storage unit (not shown). The program storage unit stores a program for combining the commands to heat the wafer in which the film of the block copolymer is formed in a solvent vapor atmosphere (refer to FIG. 1(b)) in the heating device 10. . The control unit 300 outputs a command signal to the component or member such as the power source 204P, the solvent vapor supply mechanism 270, and the injector 275 according to the program, and controls the power supplied from the power source 204P to the heating unit 204h and the solvent vapor supply mechanism 270. The flow rate and concentration of the solvent vapor supplied from the flow controller 272 and the gasifier 273, and the amount of exhaust gas of the solvent vapor-containing gas exhausted from the processing chamber 220 by the ejector 275, and the like. The program is stored in the program storage unit, for example, in a state of a memory medium such as a hard disk, a compact disk, a magneto-optical disk, or a memory card.

According to the above configuration, the solvent vapor generated from the solvent vapor supply mechanism 270 is supplied to the processing chamber 220 through the pipe 261 and the gas supply path 233, and the wafer W heated by the heating portion 204h is uniformly supplied by the rectifying plate 234. Then, the solvent vapor is exhausted by the ejector 275 through the exhaust passage 281, the cavity portion 282, and the exhaust pipe 283. The gas discharged from the ejector 275 reaches the supply tank 276 where the solvent component in the gas is removed and exhausted to the outside. Further, the pressure in the processing chamber 220 can be controlled by the supply amount of the supplied solvent vapor and the ejector 275, and for example, it is preferably maintained at a normal pressure or a pressure of a normal pressure of 0 Pa to 30 kPa (weak positive pressure).

According to the heating device 10 having the above configuration, the wafer W can be added in a solvent vapor environment. heat. Therefore, phase separation can be promoted by promoting fluidization of the polymer of the block copolymer.

The present invention has been described with reference to the preferred embodiments of the present invention. However, the present invention is not limited thereto, and various modifications and changes can be made within the scope of the invention as described in the appended claims.

For example, when the film of the block copolymer is heated in a solvent vapor atmosphere, the concentration of the solvent vapor (the vapor containing the mixed solvent described below) in the gas atmosphere around the wafer W may be gradually lowered. Further, for example, a solvent vapor atmosphere may be formed by a mixed solvent in which at least two of toluene, acetone, ethanol, methanol, and cyclohexanone are mixed. Further, toluene having a large solubility to the PS-b-PMMA block copolymer may be used for heating, followed by use of acetone having a small solubility. Thereby, in the initial stage, the fluidity of the PS polymer and the PMMA polymer is increased to be phase separated at an early stage, and the PS polymer and the PMMA polymer are respectively aggregated to a certain extent to lower the fluidity, thereby simply Configured as the desired pattern. Further, the same effect can be obtained by lowering the temperature during heating. For example, the temperature during heating may be lowered stepwise or gradually from about 300 ° C to about 100 ° C.

Further, the heating period may be divided into the first to third periods depending on the type of the solvent. For example, in the first period, the film of the block copolymer is heated in a vapor atmosphere of only toluene; in the second period, the film of the block copolymer is heated in a vapor atmosphere of a mixed solvent of toluene and acetone; During the period of 3, the film of the block copolymer was heated in a vapor atmosphere of only acetone. Further, in the second period, the concentration of toluene in the mixed solvent of toluene and acetone may be 50% (the concentration of acetone is also 50%). Further, in the second period, the concentration of toluene may be changed from 100% to 0%, and the concentration of acetone may be changed from 0% to 100%.

When two or more types of solvents are used, instead of storing the mixed solvent such as the solvent in the solvent tank 271, a plurality of solvent vapor supply mechanisms 270 corresponding to the solvent may be provided. In this case, the plurality of solvent vapor supply mechanisms 270 can be controlled by the control unit 300. Thereby, the control unit 300 can control each of the solvent vapor supply mechanisms 270 to easily perform the change of the solvent to be used or the change in the solvent concentration.

Further, in the above-described embodiment, the gas atmosphere around the wafer W is a mixed gas atmosphere of toluene vapor and nitrogen gas, but a rare gas such as argon gas or helium gas or clean air may be used instead of nitrogen gas.

Further, in the above-described embodiment, PS-b-PMMA is exemplified as the block copolymer, but is not limited thereto, and examples thereof include polybutadiene-polydimethylsiloxane and polybutadiene-4-. Vinyl pyridine, polybutadiene-methyl methacrylate, polybutadiene-polybutyl methacrylate, polybutadiene-tert-butyl acrylate, polybutyl methacrylate-poly- 4-vinylpyridine, polyethylene-polymethyl methacrylate, polybutyl methacrylate-poly-2-vinylpyridine, polyethylene-poly-2-vinylpyridine, polyethylene-poly-4-vinylpyridine , polyisoprene-poly-2-vinylpyridine, polymethyl methacrylate-polystyrene, polybutyl methacrylate-polystyrene, polymethyl acrylate-polystyrene, polybutylene Alkene-polystyrene, polyisoprene-polystyrene, polystyrene-poly-2-vinylpyridine, polystyrene-poly-4-vinylpyridine, polystyrene-polydimethyloxane, Polystyrene-poly-N,N-dimethyl decylamine, polybutadiene-polyacrylate, polybutadiene-polyethylene oxide, polybutyl methacrylate-poly epoxy Alkane, polystyrene-polypropylene Acid, polystyrene-polymethacrylic acid, and the like.

Particularly in block copolymers composed of an organic polymer and an inorganic polymer such as polystyrene-polydimethyloxane (PS-b-PDMS), the block copolymerization is used because of low fluidity. In the case of the object, the embodiment of the present invention can be suitably applied.

Further, the solvent vapor supply mechanism 270 may have a bubbler that generates solvent vapor by bubbling the stored solvent with a carrier gas instead of the solvent tank 271, the flow rate controller 272, and the vaporizer 273. And a controller that controls the flow rate of the carrier gas containing the solvent vapor.

In the above-described pattern forming method, the temperature, the heating time, and the like of the heated wafer W are exemplified, but the present invention is not limited thereto, and the heating temperature, the heating time, and the like may be set by a preliminary experiment or the like.

21‧‧‧ film

DS‧‧‧PS polymer area

F‧‧‧heating device

HP‧‧‧ heating plate

L‧‧‧Light source

OS‧‧‧Organic solvent

W‧‧‧ wafer

Claims (16)

A pattern forming method comprising the steps of: forming a film of a block copolymer containing at least two polymers on a substrate; heating the film of the block copolymer in a solvent vapor atmosphere to give the block copolymer a step of phase separation; and a step of removing one of the films of the block copolymer in which the phase separation has been completed. The pattern forming method according to claim 1, wherein in the step of separating the phases, the partial pressure of the solvent vapor in the solvent vapor environment is continuously or stepwise decreased. The pattern forming method according to claim 1 or 2, wherein in the step of separating the phase, the vapor of the first solvent and the vapor of the second solvent are contained in the solvent vapor atmosphere. The pattern forming method according to claim 3, wherein a ratio of a partial pressure of the vapor of the first solvent to a partial pressure of the vapor of the second solvent changes with time. The pattern forming method according to claim 1 or 2, wherein in the step of separating the phase, the solvent vapor in the solvent vapor atmosphere is changed from the vapor of the third solvent to the vapor of the fourth solvent. The pattern forming method according to claim 1 or 2, wherein in the step of separating the phases, the temperature of the film which heats the block copolymer is lowered. The pattern forming method according to claim 1 or 2, wherein after the step of separating the phase, the step of heating the film of the block copolymer in an inert gas atmosphere to dry the film is further included. The pattern forming method of claim 7, wherein the temperature in the drying step is higher than the temperature in the step of separating the phases. A heating device comprising: a mounting table; a substrate placed in a container and having a film on which a block copolymer is formed; and a heating unit built in the mounting table to heat the substrate placed on the mounting table; The solvent vapor supply unit supplies a gas containing the solvent vapor into the container, and an exhaust unit that exhausts the gas in the container. The heating device according to claim 9, further comprising a control unit that controls the solvent vapor supply unit to continuously or stepwise decrease a partial pressure of the vapor of the solvent in the solvent vapor-containing gas. The heating device of claim 9 or 10, wherein the vapor of the solvent comprises a vapor of the first solvent and a vapor of the second solvent. The heating device according to claim 9 or 10, wherein the solvent vapor supply unit supplies a gas containing the vapor of the first solvent to the container; and the heating device further includes: an additional solvent vapor supply unit, which includes The gas of the vapor of the second solvent is supplied into the container; and the control unit controls the solvent vapor supply unit and the additional solvent vapor supply unit to make the partial pressure of the vapor of the first solvent and the vapor of the second solvent. The ratio of partial pressures changes over time. The heating device according to claim 12, wherein the control unit controls the solvent vapor supply unit and the additional solvent vapor supply unit to supply the solvent to the solvent vapor-containing gas in the container. The vapor is changed from the vapor of the first solvent to the vapor of the second solvent. The heating device according to claim 9 or 10, further comprising a control unit that controls the heating unit to lower the temperature of the film that heats the block copolymer. A heating device according to claim 9 or 10, wherein the heating portion heats the film of the block copolymer on the substrate under an inert gas atmosphere. The heating device of claim 15, wherein the film of the block copolymer is dried at a higher temperature than when the film of the block copolymer is heated.