WO2015075833A1 - パターン形成方法及び加熱装置 - Google Patents
パターン形成方法及び加熱装置 Download PDFInfo
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- WO2015075833A1 WO2015075833A1 PCT/JP2013/081617 JP2013081617W WO2015075833A1 WO 2015075833 A1 WO2015075833 A1 WO 2015075833A1 JP 2013081617 W JP2013081617 W JP 2013081617W WO 2015075833 A1 WO2015075833 A1 WO 2015075833A1
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- 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
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C9/00—Apparatus or plant for applying liquid or other fluent material to surfaces by means not covered by any preceding group, or in which the means of applying the liquid or other fluent material is not important
- B05C9/08—Apparatus or plant for applying liquid or other fluent material to surfaces by means not covered by any preceding group, or in which the means of applying the liquid or other fluent material is not important for applying liquid or other fluent material and performing an auxiliary operation
- B05C9/14—Apparatus or plant for applying liquid or other fluent material to surfaces by means not covered by any preceding group, or in which the means of applying the liquid or other fluent material is not important for applying liquid or other fluent material and performing an auxiliary operation the auxiliary operation involving heating or cooling
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/38—Treatment before imagewise removal, e.g. prebaking
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- 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
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02118—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer carbon based polymeric organic or inorganic material, e.g. polyimides, poly cyclobutene or PVC
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
- H01L21/02318—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment
- H01L21/02337—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment treatment by exposure to a gas or vapour
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- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31127—Etching organic layers
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- H01L21/31138—Etching organic layers by chemical means by dry-etching
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- H01L21/67005—Apparatus not specifically provided for elsewhere
- H01L21/67011—Apparatus for manufacture or treatment
- H01L21/67098—Apparatus for thermal treatment
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- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/67005—Apparatus not specifically provided for elsewhere
- H01L21/67011—Apparatus for manufacture or treatment
- H01L21/67098—Apparatus for thermal treatment
- H01L21/67115—Apparatus for thermal treatment mainly by radiation
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- H—ELECTRICITY
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- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
- H01L21/687—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using mechanical means, e.g. chucks, clamps or pinches
- H01L21/68714—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using mechanical means, e.g. chucks, clamps or pinches the wafers being placed on a susceptor, stage or support
- H01L21/68742—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using mechanical means, e.g. chucks, clamps or pinches the wafers being placed on a susceptor, stage or support characterised by a lifting arrangement, e.g. lift pins
Definitions
- the present invention relates to a self-organizing (DSA) lithography technique, and to a pattern forming method and a heating apparatus using this technique.
- DSA self-organizing
- Patent Documents 1 and 2 and Non-Patent Document 1 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).
- 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.
- 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.
- the phase separation of the block copolymer is realized by fluidizing the A polymer and the B polymer by heating, collecting the A polymers, and collecting the B polymers.
- the present invention provides a pattern forming method and a heating apparatus that can promote phase separation by promoting fluidization of a block copolymer polymer.
- a pattern forming method for forming a pattern on a substrate comprising: forming a block copolymer film containing at least two polymers on the substrate; and Heating the copolymer film under a solvent vapor atmosphere to phase-separate the block copolymer; and removing one polymer from the phase-separated block copolymer film.
- the present invention is a heating apparatus for heating a substrate, the mounting table being placed in a container and 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 heats the substrate mounted on the mounting table, a solvent vapor supply unit that supplies a gas containing solvent vapor into the container, and the gas in the container And an exhaust part for exhausting the air.
- a pattern forming method and a heating device that can promote phase separation by promoting fluidization of a polymer of a block copolymer.
- (A)-(e) is explanatory drawing explaining the pattern formation method by embodiment of this invention for every process.
- (A) to (c) are surface images of patterns formed according to the pattern forming method according to the embodiment of the present invention. It is a schematic block diagram of the heating apparatus by embodiment of this invention.
- 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.
- a polystyrene (PS) -polymethyl methacrylate (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.
- a solution dissolved in hereinafter also referred to as a coating solution
- 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.
- the wafer W on which the PS-b-PMMA film 21 is formed is carried into the heating apparatus F and placed on the hot plate HP.
- 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. Note that it is preferable to form a guide pattern on the surface of the wafer W in order to arrange the PS polymer region DS and PMMA polymer region DM of PS-b-PMMA in a predetermined pattern.
- the solvent is not particularly limited as long as the PS polymer and the PMMA polymer can be dissolved, and for example, toluene, acetone, ethanol, methanol, and cyclohexanone can be used.
- steam atmosphere can be produced
- 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 in the range of about 150 ° C. to about 350 ° C.
- 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.
- an inert gas a rare gas such as nitrogen gas, argon gas or helium gas
- 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.
- 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.
- ultraviolet light will not be specifically limited if it has the wavelength component which belongs to an ultraviolet light area
- an Xe excimer lamp that emits ultraviolet light having a wavelength of 172 nm can be suitably used as the light source L.
- the PS-b-PMMA film 21 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. On the other hand, in PMMA, the main chain is cleaved. It is thought that it becomes easy to dissolve in a solvent.
- the irradiation intensity is preferably about 180 mJ or less.
- 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.
- 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.
- the oxygen concentration in the atmosphere around the wafer W is lowered by the inert gas.
- the oxygen concentration in the inert gas atmosphere is, for example, 400 ppm or less.
- an 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.
- the organic solvent OS for example, isopropyl alcohol (IPA) can be preferably used.
- 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.
- 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.
- the pattern formation method of this embodiment since the film
- 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.
- SEM scanning electron microscope
- FIG. 2A shows a pattern (PS polymer region DS) formed by heating the wafer W in air at atmospheric pressure for comparison.
- FIG. 3 is a schematic configuration diagram of the heating device.
- the heating device 10 includes a cylindrical container body 202 having an upper end opening and a bottom, and a lid 203 that covers the upper end opening of the container 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.
- 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).
- the peripheral portion 231 of the lid 203 is 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 pipe 261 connected to a solvent vapor supply mechanism 270 described later is connected to the gas supply path 233.
- 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).
- the solvent vapor supplied to the processing chamber 220 through the gas supply path 233 spreads laterally on the upper side of the rectifying plate 234, that is, toward the outer periphery of the lid 203, and toward the wafer W through the slit 234S. Flowing. Accordingly, the solvent vapor can be supplied to the wafer W at a substantially uniform concentration.
- 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.
- 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.
- 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.
- 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
- 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 vaporized.
- 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.
- 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.
- the controller 300 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.
- 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.
- 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.
- the wafer W can be heated under a solvent vapor atmosphere. Therefore, phase separation can be promoted by promoting fluidization of the block copolymer polymer.
- 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.
- 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.
- the temperature during heating may be decreased stepwise or gradually from about 300 ° C to about 100 ° C.
- the heating period may be divided into first to third periods according to the type of solvent.
- the block copolymer film 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.
- the block copolymer film in the third period, the block copolymer film may be heated in a vapor atmosphere of only acetone.
- the concentration of toluene in the mixed solvent of toluene and acetone may be 50% (the concentration of acetone is also 50%).
- the concentration of toluene may be changed from 100% to 0%, and the concentration of acetone may be changed from 0% to 100%.
- 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.
- 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.
- the atmosphere around the wafer W is a mixed gas atmosphere of toluene vapor and nitrogen gas.
- nitrogen gas a rare gas such as argon gas or helium gas, or clean air is used. It may be used.
- PS-b-PMMA is exemplified as the block copolymer.
- the present invention is not limited thereto, and examples thereof include polybutadiene-polydimethylsiloxane, polybutadiene-4-vinylpyridine, and polybutadiene-methyl methacrylate.
- a block copolymer composed of an organic polymer and an inorganic polymer such as polystyrene-polydimethylsiloxane (PS-b-PDMS) has low fluidity.
- PS-b-PDMS polystyrene-polydimethylsiloxane
- 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.
- the temperature for heating the wafer W, the heating time, and the like are exemplified, but the present invention is not limited thereto, and it is needless to say that the heating temperature, the heating time, and the like may be set through a preliminary experiment or the like. .
Abstract
Description
次に、基板を加熱すると、薄膜中で互いにランダムに固溶していたAポリマー鎖とBポリマー鎖が相分離し、規則的に配列されるAポリマー領域とBポリマー領域とが形成される。
まず、例えばスピン塗布法により、基板としての半導体ウエハ(以下、単にウエハ)W上に、ポリスチレン(PS)-ポリメチルメタクリレート(PMMA)ブロック共重合体(以下、PS-b-PMMA)を有機溶媒に溶解した溶液(以下、塗布液とも言う)を塗布すると、図1(a)に示すように、PS-b-PMMAの膜21が形成される。この膜21においては、PSポリマーとPMMAポリマーとが互いにランダムに混ざり合っている。
図2(a)及び図2(b)は、PS-b-PMMAを用いて形成したパターンの上面を撮像した走査型電子顕微鏡(SEM)像である。具体的には、図1(e)に示すPSポリマー領域DSからなるパターンの上面を示している。なお、これらのパターンを形成したときには、ガイドパターンを用いなかったため、指紋状のパターンとなっている。
204 ウエハ載置台
204h 加熱部
234 整流板
261 配管
233 ガス供給路
220 処理室
234 整流板
281 排気路
282 空洞部
283 排気管
270 溶剤蒸気供給機構
271 溶剤タンク
272 流量制御器
273 気化器
275 エジェクタ
276 トラップタンク
W ウエハ
Claims (16)
- 基板上にパターンを形成するパターン形成方法であって、
少なくとも二つのポリマーを含むブロック共重合体の膜を基板に形成するステップと、
前記ブロック共重合体の膜を溶剤蒸気雰囲気の下で加熱して、前記ブロック共重合体を相分離させるステップと、
相分離された前記ブロック共重合体の膜のうち一のポリマーを除去するステップと、を有する。 - 請求項1に記載のパターン形成方法において、
前記相分離させるステップにおいて、前記溶剤蒸気雰囲気中の溶剤蒸気の分圧を連続的に又は段階的に低下させる。 - 請求項1に記載のパターン形成方法において、
前記相分離させるステップにおいて、前記溶剤蒸気雰囲気に第1の溶剤の蒸気と第2の溶剤の蒸気とが含まれる。 - 請求項3に記載のパターン形成方法において、
前記第1の溶剤の蒸気の分圧と、前記第2の溶剤の蒸気の分圧との比を経時的に変化させる。 - 請求項1に記載のパターン形成方法において、
前記相分離させるステップにおいて、前記溶剤蒸気雰囲気中の溶剤蒸気を第3の溶剤の蒸気から第4の溶剤の蒸気に変更する。 - 請求項1に記載のパターン形成方法において、
前記相分離させるステップにおいて、前記前記ブロック共重合体の膜を加熱する温度を低下させる。 - 請求項1に記載のパターン形成方法において、
前記相分離させるステップの後に、前記ブロック共重合体の膜を不活性ガス雰囲気の下で加熱し、前記膜を乾燥させるステップをさらに有する。 - 請求項7に記載のパターン形成方法において、
前記乾燥させるステップにおける温度が前記相分離させるステップにおける温度よりも高い。 - 基板を加熱する加熱装置であって、
容器内に配置され、ブロック共重合体の膜が形成される基板が載置される載置台と、
前記載置台に内蔵され、当該載置台に載置される前記基板を加熱する加熱部と、
溶剤の蒸気を含む気体を前記容器内に供給する溶剤蒸気供給部と、
前記容器内の前記気体を排気する排気部と、を有する。 - 請求項9に記載の加熱装置において、
前記溶剤蒸気供給部を制御して、前記溶剤の蒸気を含む気体中の前記溶剤の蒸気の分圧を連続的に又は段階的に低下させる制御部をさらに有する。 - 請求項9に記載の加熱装置において、
前記溶剤の蒸気が、第1の溶剤の蒸気と第2の溶剤の蒸気とを含む。 - 請求項9に記載の加熱装置において、
前記溶剤蒸気供給部が第1の溶剤の蒸気を含む気体を前記容器内に供給し、
第2の溶剤の蒸気を含む気体を前記容器内に供給する追加の溶剤蒸気供給部と、
前記溶剤蒸気供給部及び前記追加の溶剤蒸気供給部を制御して、前記第1の溶剤の蒸気の分圧と、前記第2の溶剤の蒸気の分圧との比を経時的に変化させる制御部と、をさらに有する。 - 請求項12に記載の加熱装置において、
前記制御部が、前記溶剤蒸気供給部及び前記追加の溶剤蒸気供給部を制御して、前記容器内に供給される前記溶剤の蒸気を含む気体中の前記溶剤の蒸気を第1の溶剤の蒸気から第2の溶剤の蒸気に変更する。 - 請求項9に記載の加熱装置において、
前記加熱部を制御して、前記前記ブロック共重合体の膜を加熱する温度を低下させる制御部をさらに有する。 - 請求項9に記載の加熱装置において、
前記加熱部は、前記基板上の前記ブロック共重合体の膜を不活性ガス雰囲気の下で加熱する。 - 請求項15に記載の加熱装置において、
前記ブロック共重合体の膜を乾燥させるときの温度が前記ブロック共重合体の膜を加熱するときの温度よりも高い。
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