JP5748708B2 - Pattern forming method and heating apparatus - Google Patents

Pattern forming method and heating apparatus Download PDF

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JP5748708B2
JP5748708B2 JP2012126591A JP2012126591A JP5748708B2 JP 5748708 B2 JP5748708 B2 JP 5748708B2 JP 2012126591 A JP2012126591 A JP 2012126591A JP 2012126591 A JP2012126591 A JP 2012126591A JP 5748708 B2 JP5748708 B2 JP 5748708B2
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solvent vapor
block copolymer
solvent
heating
film
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JP2013249430A (en
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村松 誠
誠 村松
北野 高広
高広 北野
忠利 冨田
忠利 冨田
啓士 田内
啓士 田内
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東京エレクトロン株式会社
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Description

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

  The practical application of self-organized lithography technology using the property that block copolymers are arranged in a self-organized manner has been studied (for example, Patent Documents 1 and 2 and Non-Patent Document 1). In the self-organized lithography technique, first, for example, a solution of a block copolymer including an A polymer chain and a B polymer chain is applied to a substrate to form a thin film of the block copolymer. Next, when the substrate is heated, the A polymer chain and the B polymer chain that are randomly dissolved in each other in the thin film are phase-separated to form regularly arranged A polymer regions and B polymer regions.

  Phase separation of the block copolymer is realized by heating the A polymer and the B polymer to flow, the A polymers gathering, and the B polymers gathering.

JP 2005-29779 A JP 2007-125699 A

K. W. 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 thin film of the block copolymer is formed is heated and the block copolymer is phase-separated to form the A polymer region and the B polymer region, generally, the higher the heating temperature, the longer the heating time, Phase separation is sure to occur. However, when the heating temperature is too high, there is a problem that the solvent of the A polymer and the B polymer evaporates, making it difficult for each to flow, and the A polymer and / or the B polymer evaporate. Further, when the heating time is lengthened, there arises a problem that the production throughput is lowered.

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

According to a first aspect of the present invention, a step of forming a block copolymer film containing at least two polymers on a substrate, and the block copolymer film under a solvent vapor atmosphere, the block copolymer is formed. Forming a pattern comprising: heating at a temperature higher than the glass transition temperature of the block copolymer to phase-separate the block copolymer; and removing one polymer from the phase-separated film of the block copolymer A method is provided.

According to the second aspect of the present invention, a mounting table placed in a container and on which a substrate on which a film of a block copolymer is formed is mounted, and is built in the mounting table and mounted on the mounting table. A heating unit for heating the substrate to be heated at a temperature higher than the glass transition temperature of the block copolymer , a solvent vapor supply unit for supplying a gas containing a solvent vapor into the container, There is provided a heating device including an exhaust part for exhausting the gas.

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

It is explanatory drawing explaining the pattern formation method by embodiment of this invention. It is the surface image of the pattern formed in accordance with the pattern formation method by embodiment of this invention. It is a schematic block diagram of the heating apparatus by embodiment of this invention.

  Hereinafter, exemplary embodiments of the present invention will be described with reference to the accompanying drawings. In all the accompanying drawings, the same or corresponding members or parts are denoted by the same or corresponding reference numerals, and redundant description is omitted.

FIG. 1 shows a partial cross section at each step of a substrate (for example, a semiconductor wafer) processed by a pattern forming method according to an embodiment of the present invention.
First, a polystyrene (PS) -polymethylmethacrylate (PMMA) block copolymer (hereinafter referred to as PS-b-PMMA) is placed on an organic solvent on a semiconductor wafer (hereinafter simply referred to as wafer) W as a substrate by, for example, spin coating. When a solution dissolved in (hereinafter also referred to as a coating solution) is applied, a PS-b-PMMA film 21 is formed as shown in FIG. In this film 21, the PS polymer and the PMMA polymer are randomly mixed with each other.

  Next, as shown in FIG. 1B, the wafer W on which the PS-b-PMMA film 21 is formed is loaded into the heating device F and placed on the hot plate HP. When the wafer W is heated at a predetermined temperature under a solvent vapor atmosphere by the hot plate HP, phase separation occurs in PS-b-PMMA in the film 21 on the wafer W. The PS polymer region DS and the PMMA polymer region DM are alternately arranged by phase separation. In order to arrange the PS polymer region DS and the PMMA polymer region DM of PS-b-PMMA in a predetermined pattern, it is preferable to form a guide pattern on the surface of the wafer W.

Here, as a solvent, if PS polymer and PMMA polymer are soluble, it will not specifically limit, For example, toluene, acetone, ethanol, methanol, cyclohexanone, etc. can be used. Moreover, a solvent vapor | steam atmosphere can be produced | generated in the heating apparatus F by atomizing a solvent using an atomizer, for example, and transporting spray of a solvent in the heating apparatus F with an inert gas.
Further, the temperature of the film 21 during heating is preferably higher than the glass transition temperature of PS-b-PMMA, and may be, for example, a temperature ranging from about 150 ° C. to about 350 ° C.

  After a predetermined time has elapsed, the supply of solvent vapor into the heating device F is stopped, and the film 21 is dried under an atmosphere of an inert gas (a rare gas such as nitrogen gas, argon gas or helium gas), The PS-b-PMMA film 21 is further heated. Thereby, the solvent (and solvent) in the film 21 is evaporated. Note that 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 at the time of drying.

  After the heating, as shown schematically in FIG. 1C, a rare gas such as argon (Ar) or helium (He) or nitrogen gas is applied to the PS-b-PMMA film 21 on the wafer W. Ultraviolet light is irradiated in an inert gas atmosphere. Although ultraviolet light will not be specifically limited if it has the wavelength component which belongs to an ultraviolet light area | region, For example, it is preferable to have a wavelength component of 200 nm or less. Further, it is more preferable that the ultraviolet light includes a wavelength component of 185 nm or less that can be absorbed by PMMA. When using ultraviolet light having a wavelength component of 200 nm or less, an Xe excimer lamp that emits ultraviolet light having a wavelength of 172 nm can be suitably used as the light source L.

  When the PS-b-PMMA film 21 is irradiated with ultraviolet light, a cross-linking reaction occurs in PS, so that PS hardly dissolves in an organic solvent, whereas in PMMA, the main chain is cut, so PMMA is organic. It is thought that it becomes easy to dissolve in a solvent. When ultraviolet light having a wavelength of 172 nm is used, the irradiation intensity (dose amount) is preferably about 180 mJ or less. When the PS-b-PMMA film 21 is irradiated with ultraviolet light having a wavelength of 172 nm with a dose amount greater than 180 mJ, when the organic solvent is supplied to the PS-b-PMMA film 21 later, the organic solvent becomes the PS polymer region DS. This is because the PS polymer region DS swells and the PMMA polymer region DM becomes difficult to be removed. Furthermore, when the dose amount of ultraviolet light is larger than 180 mJ, the PMMA polymer region DM may be denatured and solidified, and may not be easily dissolved in an organic solvent.

  Although the oxygen concentration in the atmosphere around the wafer W is reduced by the inert gas, specifically, the oxygen concentration in the inert gas atmosphere is, for example, 400 ppm or less.

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

  When the surface of the wafer W is dried after a predetermined time has elapsed, a pattern of the PS polymer region DS is obtained on the surface of the wafer W as shown in FIG.

  According to the pattern forming method according to the present embodiment described above, since the PS-b-PMMA film 21 is heated in a solvent vapor atmosphere, the solvent can be absorbed by the film 21 being heated. For this reason, even if the solvent remaining in the film 21 evaporates during heating, the absorbed solvent suppresses the concentration of the PS polymer and the PMMA polymer (with respect to the solvent and the solvent) in the film 21 from being lowered. Therefore, the fluidity of the PS polymer and PMMA polymer is maintained, and phase separation can be facilitated. Therefore, phase separation can be promoted by promoting fluidization of PS-b-PMMA.

  For example, when the film 21 is heated in an air atmosphere, the solvent remaining in the film 21 may evaporate and the fluidity of the PS polymer and PMMA polymer may be lost. It must be about 150 ° C. or lower. At temperatures as low as this, phase separation takes time and throughput decreases. On the other hand, according to the pattern formation method of this embodiment, since the film | membrane 21 is heated under a solvent vapor | steam atmosphere, heating temperature can be made high. Thereby, it becomes possible to further promote phase separation.

Next, the result of forming a pattern by the PS polymer region DS formed according to the above-described pattern forming method will be described with reference to FIG.
2A and 2B are scanning electron microscope (SEM) images obtained by imaging the upper surface of a pattern formed using PS-b-PMMA. Specifically, the upper surface of the pattern composed of the PS polymer region DS shown in FIG. When these patterns are formed, the guide pattern is not used, and thus a fingerprint-like pattern is formed.

  In the pattern shown in FIG. 2A, when the PS-b-PMMA film 21 is heated (FIG. 1B), the atmosphere around the wafer W is a toluene vapor atmosphere. At this time, the partial pressure of toluene was about 15 Torr (normal pressure using toluene and nitrogen gas at this partial pressure). In the pattern shown in FIG. 2B as well, when the PS-b-PMMA film 21 is heated, the atmosphere around the wafer W is a toluene vapor atmosphere. At this time, the partial pressure of toluene was about 30 Torr. FIG. 2C shows a pattern (PS polymer region DS) formed by heating the wafer W in air at atmospheric pressure for comparison. Comparing these SEM images, it can be seen that a clearer pattern can be obtained in a short time when the wafer W (and the film 21) is heated in an atmosphere of toluene vapor. This is presumably because the fluidity of the PS polymer and PMMA polymer in the PS-b-PMMA film 21 was improved by toluene vapor compared to the case of air alone.

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

  Referring to FIG. 3, the heating device 10 includes a cylindrical container main body 202 having an upper end opening and a bottom, and a lid 203 that covers the upper end opening of the container main body 202. The container body 202 includes an annular frame 221, a bowl-shaped bottom 222 extending inward from the bottom of the frame 221, and a wafer mounting table 204 supported by the bottom 222. A heating unit 204h is provided inside the wafer mounting table 204, and a power source 204P is connected to the heating unit 204h. As a result, the wafer W placed on the wafer placement table 204 is heated. The wafer mounting table 204 is heated and the wafer W mounted on the wafer mounting table 204 is heated by the heating unit 204h, the power source 204P, and a temperature controller (not shown).

  The wafer mounting table 204 is provided with a plurality of lifting pins 241 for transferring the wafer W to and from an external transfer means (not shown). The lifting pins 241 can be lifted and lowered by a lifting mechanism 242. It is configured. Reference numeral 243 in the figure is a cover body that is provided on the back surface of the wafer mounting table 204 and surrounds the periphery of the elevating mechanism 242. The container main body 202 and the lid body 203 are configured to be movable up and down relative to each other. In this example, the lid 203 can be moved up and down between a processing position connected to the container main body 202 and a substrate loading / unloading position located above the container main body 202 by an elevating mechanism (not shown).

  On the other hand, the lid 203 has a peripheral portion 231 of the lid 203 placed on the upper surface of the frame 221 of the container body 202 via a seal member 202S such as an O-ring. Thereby, the upper end opening of the container body 202 is closed by the lid 203. A processing chamber 220 is defined between the container body 202 and the lid body 203.

  A gas supply path 233 for supplying a gas containing solvent vapor (hereinafter simply referred to as solvent vapor) to the wafer W placed on the wafer placement table 204 penetrates through the center of the lid 203. Yes. A pipe 261 connected to a solvent vapor supply mechanism 270 described later is connected to the gas supply path 233. Further, a nitrogen gas supply source (not shown) for purging the processing chamber 220 is connected to the pipe 261 so that nitrogen gas as a purge gas can be supplied to the processing chamber 220.

  A rectifying plate 234 is disposed below the lower end of the gas supply path 233. The rectifying plate 234 is formed with a plurality of slits (or openings) 234S. The plurality of slits 234S allow the solvent vapor flowing out from the gas supply path 233 to flow toward the wafer mounting table 204, and the space on the upper side (gas supply path 233 side) and lower side (wafer mounting) of the rectifying plate 234. It is formed so that a large pressure difference is generated between the space on the stage 204 side). Therefore, the solvent vapor supplied to the processing chamber 220 through the gas supply path 233 spreads laterally (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. . Accordingly, the solvent vapor can be supplied to the wafer W at a substantially uniform concentration.

Further, in the upper wall portion 232 of the lid 203, a flat hollow portion 282 having a planar shape extending in a plane shape, for example, in a region other than the central region where the gas supply path 233 is formed is formed. ing. An exhaust path 281 that extends in the vertical direction on the outer peripheral side of the lid 203 and outside the wafer W on the wafer mounting table 204 and opens to the processing chamber 220 is connected to the cavity 282. In addition, a plurality of (for example, six) exhaust pipes 283 are connected to the hollow portion 282, for example, in a region near the center of the lid 203. The exhaust pipe 283 is connected to the ejector 275, and the ejector 275 is connected to the trap tank 276.
Note that reference numeral 235 in FIG. 3 indicates a heater, and the lid 203 is heated to a predetermined temperature by the heater 235. Thereby, condensation of the solvent vapor to the lid 203 is suppressed.

  The solvent vapor supply mechanism 270 includes a solvent tank 271, a flow rate controller 272, and a vaporizer 273. The solvent is stored inside the solvent tank 271, and when the inside is pressurized with nitrogen gas from a nitrogen gas supply source (not shown), the solvent flows out to the pipe 274, and the flow rate is controlled by the flow rate controller 272 to be a vaporizer. 273. In the vaporizer 273, the solvent is atomized and supplied to the pipe 261 through the pipe 274 together with the nitrogen gas supplied from the nitrogen gas supply source.

  In addition, as shown in FIG. 3, the heating device 10 is schematically shown by parts or members constituting the heating device 10 such as a power source 204 </ b> P, a solvent vapor supply mechanism 270, an ejector 275, and a dashed line in the drawing. A control unit 300 that is electrically connected to is provided. The control unit 300 is composed of a computer, for example, and has a program storage unit (not shown). The program storage unit is instructed to cause the heating apparatus 10 to execute a heating step (see FIG. 1B) for heating the wafer on which the block copolymer film is formed in a solvent vapor atmosphere. The program is stored. Based on this program, the controller 300 outputs a command signal to components or members such as the power supply 204P, the solvent vapor supply mechanism 270, the ejector 275, and the power and solvent vapor supply mechanism supplied from the power supply 204P to the heating unit 204h. 270 controls the flow rate and concentration of the solvent vapor supplied by the flow rate controller 272 and the vaporizer 273 and the exhaust amount of the gas containing the solvent vapor exhausted from the processing chamber 220 by the ejector 275. The program is stored in the program storage unit while being stored in a storage medium such as a hard disk, a compact disk, a magnetic optical disk, or a memory card.

  With the above configuration, the solvent vapor generated by the solvent vapor supply mechanism 270 is supplied to the processing chamber 220 through the pipe 261 and the gas supply path 233, and is uniformly supplied to the wafer W heated by the heating unit 204h by the rectifying plate 234. Is done. Thereafter, the solvent vapor is exhausted by the ejector 275 through the exhaust path 281, the cavity 282, and the exhaust pipe 283. The gas exhausted by the ejector 275 reaches the trap tank 276 where the solvent component in the gas is removed and exhausted to the outside. Note that the pressure in the processing chamber 220 can be controlled by the supply amount of the solvent vapor to be supplied and the ejector 275. For example, the pressure is maintained at 0 Pa to 30 kPa (weak positive pressure) with respect to normal pressure or normal pressure. It is preferable.

  According to the heating apparatus 10 having the above-described configuration, the wafer W can be heated in a solvent vapor atmosphere. Therefore, phase separation can be promoted by promoting fluidization of the block copolymer polymer.

  The present invention has been described above with reference to the preferred embodiments of the present invention. However, the present invention is not limited to the above-described embodiments, and is within the scope of the gist of the present invention described in the claims. Various modifications and changes can be made.

  For example, when the block copolymer film is heated in a solvent vapor atmosphere, the concentration of the solvent vapor (including the following mixed solvent vapor) in the atmosphere around the wafer W may be gradually decreased. Further, for example, a solvent vapor atmosphere may be formed by a mixed solvent in which at least two of toluene, acetone, ethanol, methanol, cyclohexanone, and the like are mixed. Further, during heating, toluene having high solubility in the PS-b-PMMA block copolymer may be used, and then acetone having low solubility may be used. According to this, in the initial stage, the fluidity of the PS polymer and the PMMA polymer is increased to cause phase separation at an early stage, and after the PS polymer and the PMMA polymer are collected to a certain extent, the fluidity is lowered to obtain a desired pattern. It is possible to facilitate the arrangement. The same effect can be obtained by lowering the temperature during heating. For example, the temperature during heating may be decreased stepwise or gradually from about 300 ° C to about 100 ° C.

  Furthermore, the heating period may be divided into first to third periods depending on the type of solvent. For example, in the first period, the block copolymer film is heated under a vapor atmosphere of toluene alone, and in the second period, the block copolymer film is heated under a vapor atmosphere of a mixed solvent of toluene and acetone. In the third period, the block copolymer film may be heated in a vapor atmosphere of only acetone. Furthermore, 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 kinds of solvents are used, a plurality of solvent vapor supply mechanisms 270 corresponding to the solvents may be provided instead of storing the mixed solvent obtained by mixing them in the solvent tank 271. In this case, the plurality of solvent vapor supply mechanisms 270 can be controlled by the controller 300. According to this, each solvent vapor supply mechanism 270 is controlled by the control unit 300, and it becomes possible to easily change the solvent to be used, change the solvent concentration, and the like.

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

  In the above-described embodiment, PS-b-PMMA is exemplified as the block copolymer. However, the block copolymer is not limited thereto. For example, polybutadiene-polydimethylsiloxane, polybutadiene-4-vinylpyridine, polybutadiene-methyl methacrylate. , Polybutadiene-poly-t-butyl methacrylate, polybutadiene-t-butyl acrylate, poly-t-butyl methacrylate-poly-4-vinyl pyridine, polyethylene-polymethyl methacrylate, poly-t-butyl methacrylate-poly-2-vinyl pyridine , Polyethylene-poly-2-vinylpyridine, polyethylene-poly-4-vinylpyridine, polyisoprene-poly-2-vinylpyridine, polymethyl methacrylate-polystyrene, poly-t-butyl methacrylate -Polystyrene, polymethylacrylate-polystyrene, polybutadiene-polystyrene, polyisoprene-polystyrene, polystyrene-poly-2-vinylpyridine, polystyrene-poly-4-vinylpyridine, polystyrene-polydimethylsiloxane, polystyrene-poly-N, N- Examples include dimethylacrylamide, polybutadiene-sodium polyacrylate, polybutadiene-polyethylene oxide, poly-t-butyl methacrylate-polyethylene oxide, polystyrene-polyacrylic acid, and polystyrene-polymethacrylic acid.

  In particular, a block copolymer composed of an organic polymer and an inorganic polymer such as polystyrene-polydimethylsiloxane (PS-b-PDMS) has a low fluidity, and therefore, when such a block copolymer is used. The embodiment of the present invention can be suitably applied.

  The solvent vapor supply mechanism 270 described above includes a bubbler tank that generates solvent vapor by bubbling a stored solvent with a carrier gas, instead of the solvent tank 271, the flow rate controller 272, and the vaporizer 273, and a solvent And a controller for controlling the flow rate of the carrier gas containing the vapor.

  Further, in the pattern forming method described above, the temperature and heating time for heating the wafer W are exemplified, but not limited thereto, the heating temperature and the heating time may of course be set through a preliminary experiment or the like. .

  DESCRIPTION OF SYMBOLS 10 ... Heating device, 204 ... Wafer mounting table, 204h ... Heating part, 234 ... Current plate, 261 ... Pipe, 233 ... Gas supply path, 220 ... Processing chamber, 234 ... Rectifying plate, 281 ... Exhaust passage, 282 ... Cavity, 283 ... Exhaust pipe, 270 ... Solvent vapor supply mechanism, 271 ... Solvent tank, 272 ... Flow control 273 ... Evaporator, 275 ... Ejector, 276 ... Trap tank, W ... Wafer.

Claims (16)

  1. Forming a block copolymer film comprising at least two polymers on a substrate;
    Heating the block copolymer film at a temperature higher than the glass transition temperature of the block copolymer under a solvent vapor atmosphere to phase separate the block copolymer;
    Pattern forming method comprising the steps of removing the first polymer of the phase-separated the block copolymer of the film.
  2. Forming a block copolymer film comprising at least two polymers on a substrate;
    Heating the block copolymer membrane under a solvent vapor atmosphere to phase separate the block copolymer;
    Removing one of the phase-separated block copolymer membranes, and
    In step of the phase separation, continuously or stepwise reduce the partial pressure of solvent vapor in the solvent vapor atmosphere, pattern forming method.
  3.   The pattern forming method according to claim 1, wherein, in the phase separation step, the solvent vapor atmosphere includes a first solvent vapor and a second solvent vapor.
  4.   The pattern formation method according to claim 3, wherein a ratio between a partial pressure of the first solvent vapor and a partial pressure of the second solvent vapor is changed over time.
  5.   The pattern forming method according to claim 1, wherein in the phase separation step, the solvent vapor in the solvent vapor atmosphere is changed from a third solvent vapor to a fourth solvent vapor.
  6.   The pattern forming method according to claim 1, wherein, in the phase separating step, a temperature for heating the block copolymer film is lowered.
  7.   The pattern according to claim 1, further comprising a step of heating the block copolymer film under an inert gas atmosphere and drying the film after the phase separation step. Forming method.
  8.   The pattern forming method according to claim 7, wherein a temperature in the drying step is higher than a temperature in the phase separating step.
  9. A mounting table on which a substrate on which a film of a block copolymer is formed is placed;
    A heating unit that is built in the mounting table and that heats the substrate mounted on the mounting table at a temperature higher than the glass transition temperature of the block copolymer;
    A solvent vapor supply section for supplying a gas containing solvent vapor into the container;
    Heating device and a vent for exhausting the gas in the container.
  10. A mounting table on which a substrate on which a film of a block copolymer is formed is placed;
    A heating unit that is built in the mounting table and that heats the substrate mounted on the mounting table;
    A solvent vapor supply section for supplying a gas containing solvent vapor into the container;
    An exhaust part for exhausting the gas in the container;
    Wherein by controlling the solvent vapor supply unit, pressurized thermal device and a control unit for continuously or stepwise reduce the partial pressure of the vapor of the solvent in the gas containing the vapor of the solvent.
  11.   11. The heating apparatus according to claim 9, wherein the solvent vapor includes a first solvent vapor and a second solvent vapor.
  12. The solvent vapor supply section supplies gas containing the vapor of the first solvent into the container;
    An additional solvent vapor supply for supplying a gas containing a second solvent vapor into the vessel;
    Control for controlling the solvent vapor supply unit and the additional solvent vapor supply unit to change the ratio of the partial pressure of the first solvent vapor and the partial pressure of the second solvent vapor over time. further comprising a section, a heating apparatus according to claim 9 or 10.
  13.   The control unit controls the solvent vapor supply unit and the additional solvent vapor supply unit to convert the solvent vapor in the gas including the solvent vapor supplied into the container into the first solvent vapor. The heating device according to claim 12, wherein the heating device is changed to vapor of the second solvent.
  14.   The heating device according to any one of claims 9 to 13, further comprising a control unit that controls the heating unit to lower a temperature at which the film of the block copolymer is heated.
  15.   The heating device according to any one of claims 9 to 14, wherein the heating unit heats the block copolymer film on the substrate in an inert gas atmosphere.
  16. The heating apparatus according to claim 15, wherein a temperature at which the block copolymer film is dried is higher than a temperature at which the block copolymer film is heated.
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