WO2013146715A1 - Procédé de formation de motif - Google Patents

Procédé de formation de motif Download PDF

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Publication number
WO2013146715A1
WO2013146715A1 PCT/JP2013/058647 JP2013058647W WO2013146715A1 WO 2013146715 A1 WO2013146715 A1 WO 2013146715A1 JP 2013058647 W JP2013058647 W JP 2013058647W WO 2013146715 A1 WO2013146715 A1 WO 2013146715A1
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Prior art keywords
pattern
self
boiling point
film
forming
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PCT/JP2013/058647
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English (en)
Japanese (ja)
Inventor
永井　智樹
信也 峯岸
祐司 浪江
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Jsr株式会社
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Publication of WO2013146715A1 publication Critical patent/WO2013146715A1/fr

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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
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B81—MICROSTRUCTURAL TECHNOLOGY
    • B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
    • B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
    • B81C1/00015—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems
    • B81C1/00023—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems without movable or flexible elements
    • B81C1/00031—Regular or irregular arrays of nanoscale structures, e.g. etch mask layer
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • 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
    • G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B81—MICROSTRUCTURAL TECHNOLOGY
    • B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
    • B81C2201/00—Manufacture or treatment of microstructural devices or systems
    • B81C2201/01—Manufacture or treatment of microstructural devices or systems in or on a substrate
    • B81C2201/0101—Shaping material; Structuring the bulk substrate or layers on the substrate; Film patterning
    • B81C2201/0147—Film patterning
    • B81C2201/0149—Forming nanoscale microstructures using auto-arranging or self-assembling material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

Definitions

  • the present invention relates to a pattern forming method.
  • the present invention has been made based on the above circumstances, and its object is to provide a pattern forming method capable of reducing the occurrence of development defects by reliably selectively dissolving a part of a phase of a self-assembled film. Is to provide.
  • Pattern formation comprising a step of forming a self-assembled film having a phase separation structure using a self-assembled composition for pattern formation, and a step of removing a part of the phase of the self-assembled film using an organic solvent A method,
  • the boiling point of the organic solvent is 100 ° C. or higher.
  • the occurrence of development defects can be reduced by using the organic solvent used for removing a part of the phase of the self-assembled film as the specific solvent. This is because the use of a high-boiling organic solvent suppresses the volatilization of the organic solvent during development and suppresses the deposition of some phases of the removed self-assembled film on the pattern. This is presumed to be possible.
  • the boiling point of the organic solvent is 100 ° C. or higher, and it is difficult to volatilize. Therefore, the working environment and the like can be improved.
  • the organic solvent preferably contains at least one selected from the group consisting of hydrocarbons having 7 or more carbon atoms and ethers having 7 or more carbon atoms.
  • the self-assembling composition is preferably a composition containing two or more polymers or a composition containing a block copolymer.
  • a step of forming a lower layer film on the substrate, and a step of forming a pre-pattern on the lower layer film In the self-assembled film forming step, a self-assembled film is formed in a region on the lower film separated by the pre-pattern, After the above self-assembled film forming step, It is preferable to further include a step of removing the prepattern.
  • the phase separation of the self-assembled composition can be precisely controlled, and the resulting pattern can be further refined.
  • the pattern obtained by the pattern forming method of the present invention is preferably a line and space pattern or a hole pattern. Since the pattern forming method uses the above-described method, it is suitable for forming a fine line and space pattern or a hole pattern.
  • boiling point refers to the boiling point at 1 atmosphere.
  • boiling point is the main component (component with the largest content rate (mass%) in the components which comprise an organic solvent) among the organic solvents used together. The boiling point of the organic solvent.
  • the pattern forming method of the present invention the occurrence of development defects in the formed pattern can be reduced. Therefore, the pattern forming method can be suitably used in a lithography process in manufacturing various electronic devices such as semiconductor devices and liquid crystal devices that are required to be further miniaturized.
  • the pattern formation method of this invention it is a schematic diagram which shows an example of the state after forming a lower layer film
  • the pattern formation method of this invention it is a schematic diagram which shows an example of the state after forming a pre pattern on a lower layer film.
  • the pattern forming method of the present invention comprises: A step of forming a self-assembled film having a phase separation structure using the self-assembled composition for pattern formation (hereinafter also referred to as “self-assembled film forming step”), and a part of the phase of the self-assembled film Is removed using an organic solvent (hereinafter, also referred to as “removal step”), and preferably, a step of forming a lower layer film on the substrate (hereinafter referred to as “removal step”).
  • pre-pattern formation step A step of forming a pre-pattern on the lower layer film (hereinafter also referred to as a “pre-pattern formation step”), and a step of removing the pre-pattern after the self-assembled film formation step. (Hereinafter also referred to as “pre-pattern removal step”).
  • Directed Self-Assembly refers to a phenomenon in which an organization or structure is spontaneously constructed without being caused only by control from an external factor.
  • a film having a phase separation structure by self-organization is formed by applying a self-organizing composition for pattern formation onto a substrate and performing annealing or the like.
  • a pattern is formed by removing a part of the phase in the chemical film.
  • the boiling point of the organic solvent is 100 ° C. or higher.
  • the occurrence of development defects can be reduced by using the organic solvent used for removing a part of the phase of the self-assembled film as the specific solvent.
  • each step will be described in detail with reference to FIGS.
  • This step is a step of forming a lower layer film on the substrate using the lower layer film forming composition.
  • a substrate with a lower layer film in which the lower layer film 102 is formed on the substrate 101 can be obtained.
  • a self-assembled film is formed on the lower layer film 102.
  • the phase-separated structure (microdomain structure) of the self-assembled film is based on the interaction between different types of polymers contained in the self-assembling composition for pattern formation or the interaction between each block of the block copolymer.
  • the structure control is possible by having the lower layer film 102, and a desired pattern can be obtained.
  • the transfer process can be improved by having the lower layer film 102.
  • Examples of the substrate 101 include a silicon wafer and a wafer coated with aluminum.
  • a commercially available composition for forming an underlayer film can be used as the composition for forming an underlayer film.
  • the method for forming the lower layer film 102 is not particularly limited.
  • a coating film formed by applying the composition for forming the lower layer film on the substrate 101 by a known method such as a spin coating method is exposed and / or Alternatively, it can be formed by curing by heating.
  • the radiation used for this exposure include visible light, ultraviolet light, far ultraviolet light, X-rays, electron beams, ⁇ -rays, molecular beams, and ion beams.
  • the temperature at which the coating film is heated is not particularly limited, but is preferably 90 ° C to 550 ° C, more preferably 90 ° C to 450 ° C, and further preferably 90 ° C to 300 ° C.
  • the thickness of the lower layer film 102 is not particularly limited, but is preferably 10 nm to 20,000 nm, and more preferably 20 nm to 1,000 nm.
  • the lower layer film 102 preferably includes an SOC (Spin on carbon) film.
  • a prepattern 103 is formed on the lower layer film 102 using a composition for forming a prepattern.
  • the pre-pattern 103 controls the phase separation of the self-assembling composition for pattern formation, and a desired fine pattern can be formed. That is, among the blocks of different polymers or block copolymers contained in the self-assembling composition for pattern formation, a polymer having a high affinity with the side surface of the prepattern (hereinafter referred to as “first polymer”).
  • a block having a high affinity with the side surface of the pre-pattern forms a phase along the pre-pattern and has a lower affinity than the first polymer
  • the block having the affinity lower than that of the first block forms a phase at a position away from the pre-pattern.
  • the phase separation structure of the self-assembling composition for pattern formation can be finely controlled by the material, length, thickness, shape and the like of the prepattern.
  • the pre-pattern can be appropriately selected according to the pattern to be finally formed, and examples thereof include a line and space pattern and a hole pattern.
  • the pre-pattern 103 As a method for forming the pre-pattern 103, a method similar to a known resist pattern forming method can be used. Further, as the pre-pattern forming composition, a conventional resist film-forming composition can be used. As a specific method for forming the pre-pattern 103, for example, a commercially available chemically amplified resist composition is used and applied onto the lower layer film 102 to form a resist film. Next, a desired region of the resist film is irradiated with radiation through a mask having a specific pattern, and immersion exposure or the like is performed. Examples of the radiation include ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams.
  • the radiation include ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams.
  • the surface of the pre-pattern 103 may be subjected to a hydrophobic treatment or a hydrophilic treatment.
  • a hydrogenation treatment by exposing to hydrogen plasma for a certain period of time can be cited.
  • the pattern forming method includes the lower layer film and the pre-pattern, the phase separation of the self-assembled composition is precisely controlled, and the resulting pattern can be further refined.
  • This step is a step of forming a self-assembled film having a phase separation structure using the self-assembled composition for pattern formation.
  • the self-assembled composition for pattern formation is directly applied on the substrate to form a coating film, thereby forming a self-assembled film having a phase separation structure.
  • a pattern forming self-assembling composition is used to coat the region on the lower layer film 102 sandwiched between the prepatterns 103.
  • a film 104 is formed, and a self-assembled film 105 having a phase separation structure having an interface substantially perpendicular to the substrate 101 is formed on the lower layer film 102 formed on the substrate 101. That is, by applying a self-assembling composition for pattern formation onto a substrate and performing annealing or the like, the so-called self-organization that promotes the so-called self-organization in which sites having the same properties accumulate and form an ordered pattern spontaneously is promoted. be able to.
  • a self-assembled film having a phase separation structure such as a sea-island structure, a cylinder structure, a bicontinuous structure, or a lamella structure can be formed. These phase separation structures are substantially perpendicular to the substrate 101.
  • a phase separation structure having an interface is preferable.
  • the phase separation structure is preferably formed along the pre-pattern, and the interface formed by phase separation is more preferably substantially parallel to the side surface of the pre-pattern.
  • the phase 105b of the first polymer is formed along the side surface of the pre-pattern 103 and is adjacent to the phase 105b.
  • the second polymer phase 105a is formed, and a lamellar phase separation structure in which the first polymer phase 105b and the second polymer phase 105a are alternately arranged in this order is formed.
  • the first block is formed in parallel along the pre-pattern 103, and in the following order, the second block and the first block.
  • An alternately arranged lamellar phase separation structure or the like is formed.
  • the phase separation structure formed in this step is composed of a plurality of phases, and the interface formed from these phases is generally perpendicular to the substrate 101, but the interface itself is not necessarily clear. It's okay.
  • the method for applying the self-assembling composition for pattern formation onto a substrate is not particularly limited, and examples thereof include a method of applying by a spin coating method.
  • annealing method for example, a method of heating at a temperature of 80 ° C. to 400 ° C. by an oven, a hot plate or the like can be mentioned.
  • the annealing time is usually 30 seconds to 120 minutes, preferably 30 seconds to 90 minutes.
  • the film thickness of the self-assembled film 105 to be formed is preferably 0.1 nm to 500 nm, and more preferably 0.5 nm to 100 nm.
  • This step is a step of removing a part of the phase of the self-assembled film 105 using an organic solvent. This removal is performed by an etching process by using a difference in etching rate of each phase separated by self-organization.
  • FIG. 5 shows a state after the phase 105a and the prepattern 103 in the phase separation structure are removed.
  • the said organic solvent may be used independently and may use 2 or more types together.
  • the boiling point of the organic solvent used in the pattern forming method of the present invention is 100 ° C. or higher.
  • 110 degreeC or more is preferable, 120 degreeC or more is more preferable, and 130 degreeC or more is further more preferable.
  • 400 degrees C or less is preferable, 300 degrees C or less is more preferable, 250 degrees C or less is more preferable, 200 degrees C or less is especially preferable.
  • organic solvent for example, As chain hydrocarbons, n-octane (boiling point: 125 ° C), n-nonane (boiling point: 150 ° C), n-decane (boiling point: 174 ° C), n-undecane (boiling point: 196 ° C), 2-methylheptane (Boiling point: 116 ° C), 3-methylheptane (boiling point: 118 ° C), 2-methyloctane (boiling point: 140 ° C), 2,2-dimethylhexane (boiling point: 107 ° C), 2,2,5-trimethylhexane (Boiling point: 124 ° C.) and the like; As alicyclic hydrocarbons, cycloheptane (boiling point: 118 ° C), cyclooctane (boiling point: 149 ° C), cyclononan
  • the organic solvent is preferably a hydrocarbon and an ether, more preferably a hydrocarbon having 7 or more carbon atoms and an ether having 7 or more carbon atoms.
  • the hydrocarbon having 7 or more carbon atoms is preferably an alicyclic hydrocarbon having 7 or more carbon atoms, more preferably a saturated alicyclic hydrocarbon having 7 or more carbon atoms, cycloheptane, propylcyclohexane, isopropylcyclohexane, butylcyclohexane. T-butylcyclohexane, cyclooctane and nonane are more preferred.
  • the ether having 7 or more carbon atoms is preferably a dialkyl ether having 7 or more carbon atoms, more preferably diamyl ether, diisoamyl ether, or dihexyl ether.
  • This step is a step of removing the prepattern.
  • the pre-pattern removal method is not particularly limited, and examples thereof include a method of removing the pre-pattern by an etching process using a difference in etching rate with the formed self-assembled film 105.
  • This pre-pattern removal step can be performed after the self-assembled film forming step, and may be performed before the removal step, at the same time as the removal step or after the removal step.
  • it is preferable that a pre pattern can be easily removed with the said organic solvent.
  • the substrate is patterned by etching the lower layer film and the substrate using the pattern of the remaining phase as a mask.
  • the phase used as a mask is removed from the substrate by a dissolution process or the like, and a finally patterned substrate can be obtained.
  • the etching method a method similar to the removal step can be used, and the etching gas and the etching solution can be appropriately selected depending on the material of the lower layer film and the substrate. For example, when the substrate is made of a silicon material, a mixed gas of chlorofluorocarbon gas and SF 4 can be used.
  • the substrate is a metal film
  • a mixed gas of BCl 3 and Cl 2 or the like can be used.
  • the pattern obtained by the said pattern formation method is used suitably for a semiconductor element etc.
  • the said semiconductor element is widely used for LED, a solar cell, etc.
  • the self-assembling composition for pattern formation is a composition that forms a phase separation structure by self-organization.
  • the pattern forming self-assembled composition used in the pattern forming method of the present invention is preferably a composition containing two or more polymers or a composition containing a block copolymer.
  • the preferable pattern-forming self-assembling composition contains, for example, a component comprising two or more polymers or a component comprising a block copolymer (hereinafter also referred to as “[A] polymer component”). Moreover, the said self-organizing composition for pattern formation may contain a [B] solvent as a suitable component. Furthermore, the self-assembling composition for pattern formation may contain other components as long as the effects of the present invention are not impaired. Hereinafter, each component will be described in detail.
  • the polymer component is a polymer component that forms a phase separation structure by self-assembly.
  • This [A] polymer component is a component comprising two or more types of polymers or a block copolymer. Each will be described below.
  • the component containing two or more kinds of polymers is not particularly limited as long as the included polymers are incompatible with each other.
  • a component containing polystyrene and a poly (meth) acrylate, polystyrene examples include components containing polysiloxane.
  • the polymer of the same kind is obtained by dissolving the polymer component [A] containing such a plurality of polymers in an appropriate solvent, applying the solution to a substrate or the like to form a coating film, and then performing a treatment such as annealing. They aggregate together to form a phase consisting of the same kind of polymer. At this time, phases formed from different types of polymers do not mix with each other, so that a phase separation structure having an ordered pattern in which different types of phases are periodically and alternately repeated can be formed.
  • poly (meth) acrylate ester examples include poly (meth) acrylate methyl, poly (meth) ethyl acrylate, poly (meth) acrylate propyl, poly (meth) acrylate butyl, and poly (meth) acrylic. Acid phenyl etc. are mentioned. Note that some or all of the hydrogen atoms of the poly (meth) acrylic acid ester may be substituted with a substituent. Of these, methyl poly (meth) acrylate and phenyl poly (meth) acrylate are preferred.
  • the polysiloxane is not particularly limited as long as it is a polymer having a siloxane bond, but is preferably a hydrolysis condensate of a compound containing a hydrolyzable silane compound.
  • the polysiloxane can be synthesized using a known method. Moreover, you may use a commercial item.
  • Examples of the hydrolyzable silane compound include: Examples of the aromatic ring-containing trialkoxysilane include phenyltrimethoxysilane, phenyltriethoxysilane, 4-methylphenyltrimethoxysilane, 4-ethylphenyltrimethoxysilane, 4-hydroxyphenyltrimethoxysilane, 3-methylphenyltrimethoxysilane, 3-ethylphenyltrimethoxysilane, 3-hydroxyphenyltrimethoxysilane, 2-methylphenyltrimethoxysilane, 2-ethylphenyltrimethoxysilane, 2-hydroxyphenyltrimethoxysilane, 2,4,6-trimethylphenyltrimethoxy Silane, 4-t-butoxyphenethyltriethoxysilane, 4-t-butoxyphenyltriethoxysilane, etc .; As alkyltrialkoxysilanes, methyltrimethoxysilane,
  • an aromatic ring-containing trialkoxysilane is preferable, an aromatic ring-containing triethoxysilane is more preferable, and phenyltriethoxysilane, 4-t-butoxyphenethyltriethoxysilane, and 4-t-butoxyphenyltriethoxysilane are further included. preferable.
  • the content of the polymer other than polystyrene is 10 parts by mass to 1 part by mass with respect to 100 parts by mass of polystyrene. 1,000 parts by mass, more preferably 20 parts by mass to 500 parts by mass, and still more preferably 50 parts by mass to 200 parts by mass.
  • a pattern having a finer microdomain structure can be formed.
  • components made of block copolymer examples include a component composed of a block copolymer such as a polystyrene-poly (meth) acrylate block copolymer.
  • a component composed of a block copolymer such as a polystyrene-poly (meth) acrylate block copolymer.
  • the block copolymer will be described below using a polystyrene-poly (meth) acrylate block copolymer as an example.
  • the polystyrene-poly (meth) acrylate block copolymer exemplified here has a polystyrene block having a styrene unit and an alkyl (meth) acrylate unit. It is a block copolymer containing a poly (meth) acrylate block.
  • the block copolymer has a structure in which a plurality of blocks including at least a polystyrene block and a poly (meth) acrylate block are bonded.
  • Each of the blocks has a chain structure of one kind of monomer compound. That is, the polystyrene block has a chain structure of styrene units, and the poly (meth) acrylate block has a chain structure of alkyl (meth) acrylate units.
  • a block copolymer having a plurality of such blocks is dissolved in an appropriate solvent, applied to a substrate or the like to form a coating film, and then subjected to a treatment such as annealing, whereby the same type of blocks are Agglomerate to form a phase consisting of the same type of blocks.
  • a phase separation structure having an ordered pattern in which different types of phases are periodically and alternately repeated can be formed.
  • the block copolymer may be a block copolymer consisting of only a polystyrene block and a poly (meth) alkyl acrylate block, and in addition to the polystyrene block and the poly (meth) acrylate block, in addition to these.
  • Other block may further be included, but from the viewpoint that a pattern having a finer microdomain structure can be formed, the block copolymer is composed of only a polystyrene block and a poly (meth) acrylate block. Is preferred.
  • Examples of the (a) block copolymer consisting only of a polystyrene block and a poly (meth) acrylate block include a diblock copolymer, a triblock copolymer, and a tetrablock copolymer.
  • diblock copolymer examples include a copolymer in which a polystyrene block and a poly (meth) acrylate block are bonded.
  • triblock copolymer examples include polystyrene block-poly (meth) alkyl acrylate block-polystyrene block, poly (meth) acrylate alkyl block-polystyrene block-poly (meth) acrylate block bonded in this order. A polymer is mentioned.
  • tetrablock copolymer examples include a copolymer in which a polystyrene block, a poly (meth) acrylate block, a polystyrene block, and a poly (meth) acrylate block are bonded in this order.
  • a diblock copolymer and a triblock copolymer are preferable, a diblock copolymer is more preferable, a polystyrene block and More preferred is a diblock copolymer in which a poly (meth) acrylate alkyl block is bonded.
  • the above polystyrene block has a styrene unit and can be formed by polymerizing styrene.
  • the alkyl poly (meth) acrylate block has an alkyl (meth) acrylate unit and can be formed by polymerizing an alkyl (meth) acrylate.
  • styrene a styrene compound in which some or all of the hydrogen atoms of styrene are substituted with substituents can also be used.
  • alkyl (meth) acrylate examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth) acrylate.
  • a part or all of the hydrogen atoms of the alkyl (meth) acrylate may be substituted with a substituent. Of these, methyl methacrylate is preferred.
  • Examples of the other blocks include poly (meth) acrylic blocks other than poly (meth) acrylic acid alkyl blocks, polyvinyl acetal blocks, polyurethane blocks, polyurea blocks, polyimide blocks, polyamide blocks, Examples thereof include an epoxy block, a novolac type phenol block, and a polyester block.
  • the content ratio of the styrene unit is preferably 10 mol% to 90 mol%, more preferably 20 mol% to 80 mol%, and more preferably 30 mol% to 70 mol% with respect to all the units constituting the block copolymer (a). More preferred is mol%.
  • A By making the content rate of the styrene unit in a block copolymer into the said range, the pattern which has a finer micro domain structure can be formed.
  • the block copolymer can be synthesized by polymerizing a polystyrene block, a polymethyl methacrylate block, and other blocks other than these in a desired order by, for example, living anion polymerization, living radical polymerization, or the like. .
  • a block copolymer (a) which is a diblock copolymer composed of a polystyrene block and a polymethyl methacrylate block
  • styrene is polymerized in an appropriate solvent using an anionic polymerization initiator. This forms a polystyrene block.
  • methyl methacrylate is polymerized in the same manner to form a polymethyl methacrylate block.
  • a formation method of each block the method of dripping the solution containing a monomer in the reaction solvent containing a polymerization initiator, and making it polymerize, etc. are mentioned, for example.
  • a specific structure may be introduced into the terminal of the block copolymer using a terminal treating agent such as 1,2-butylene oxide.
  • the solvent used for the polymerization for example, As alkanes, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane and the like; Cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane; As aromatic hydrocarbons, benzene, toluene, xylene, ethylbenzene, etc .; As halogenated hydrocarbons, chlorobutanes, bromohexanes, dichloroethanes, hexamethylene dibromide, chlorobenzene, etc .; Examples of saturated carboxylic acid esters include ethyl acetate, n-butyl acetate, i-butyl acetate, and methyl propionate; As ketones, acetone, 2-butan
  • the reaction temperature in the polymerization may be appropriately determined according to the kind of the polymerization initiator, but is usually ⁇ 150 ° C. to 50 ° C., preferably ⁇ 80 ° C. to 40 ° C.
  • the reaction time is usually 5 minutes to 24 hours, preferably 20 minutes to 12 hours.
  • Examples of the polymerization initiator used in the polymerization include alkyl lithium, alkyl magnesium halide, sodium naphthalene, alkylated lanthanoid compounds, and the like. Among these, when polymerizing using styrene and methyl methacrylate as monomers, it is preferable to use alkyllithium.
  • the block copolymer is preferably recovered by a reprecipitation method. That is, the target copolymer is recovered as a powder by introducing the reaction solution into a reprecipitation solvent.
  • a reprecipitation solvent alcohols or alkanes may be used alone or in combination of two or more.
  • the block copolymer may be recovered by removing low molecular components such as monomers and oligomers by a liquid separation operation, a column operation, an ultrafiltration operation, or the like.
  • the weight average molecular weight (Mw) of the block copolymer by gel permeation chromatography (GPC) is preferably 1,000 to 150,000, more preferably 1,500 to 120,000, and 2,000. More preferable is 100,000.
  • Mw of a block copolymer By making Mw of a block copolymer into the said range, the pattern which has a finer micro domain structure can be formed.
  • the ratio (Mw / Mn) between the Mw and the number average molecular weight (Mn) of the block copolymer is usually 1 to 5, preferably 1 to 3, more preferably 1 to 2, .5 is more preferable, and 1 to 1.2 is particularly preferable.
  • the block copolymer is exemplified by a polystyrene-poly (meth) acrylate block copolymer, but the block copolymer used in the pattern forming method of the present invention is not limited to this. Absent.
  • the self-assembling composition for pattern formation usually contains a [B] solvent.
  • [B] solvent include the same solvents as those exemplified in the method for synthesizing the block copolymer (a). Of these, saturated carboxylic acid esters are preferred, and n-butyl acetate is more preferred.
  • the self-assembling composition for pattern formation may contain other components such as a surfactant as long as the effects of the present invention are not impaired.
  • a surfactant include nonionic surfactants, fluorine surfactants, and silicone surfactants. You may use these individually or in combination of 2 or more types.
  • the self-assembling composition for pattern formation can be prepared, for example, by mixing [A] a polymer component, a surfactant and the like in a predetermined ratio in a [B] solvent.
  • the solid content concentration of the self-assembling composition for pattern formation is preferably 0.01% by mass to 50% by mass, more preferably 0.05% by mass to 30% by mass, and 0.1% by mass to 10% by mass. Is more preferable.
  • the reaction solution was warmed to room temperature, concentrated, and replaced with propylene glycol methyl ether acetate (PGMEA). Thereafter, 1,000 g of a 2% by mass aqueous solution of oxalic acid was added, stirred and allowed to stand, and the lithium salt was removed by repeating the operation of removing the lower aqueous layer three times. Next, 1,000 g of ultrapure water was added and stirred, and the operation of removing the lower aqueous layer was repeated 3 times to remove oxalic acid. Then, this solution was concentrated and dropped into 500 g of n-hexane to form a polymer. Was precipitated.
  • PMEA propylene glycol methyl ether acetate
  • hydrolyzable silane compounds (M-1) to (M-3) used for the synthesis of the polymers (A2-1) to (A2-4) are shown below.
  • Et is —CH 2 —CH 3 .
  • solid content means a residue obtained by drying a sample on a hot plate at 175 ° C. for 1 hour to remove volatile substances.
  • Example 1 A composition for forming an organic underlayer film containing a crosslinking agent on a 12-inch silicon wafer was spin-coated using CLEAN TRACK ACT12 (manufactured by Tokyo Electron), and baked at 205 ° C. for 60 seconds to form a 77 nm-thick underlayer. A film was formed. Next, a resist composition containing an acid dissociable resin, a photoacid generator and an organic solvent is spin-coated on this lower layer film, and then pre-baked (PB) at 120 ° C. for 60 seconds to form a resist film having a film thickness of 60 nm. Formed.
  • PB pre-baked
  • the self-assembling composition for pattern formation (J-1) was applied to the evaluation substrate so as to have a thickness of 15 nm and heated at 120 ° C. for 1 minute to cause phase separation to form a microdomain structure. did. Thereafter, it was immersed in cycloheptane as an organic solvent for 1 minute to remove the polymer (A1-1), thereby forming a hole pattern.
  • Examples 2 to 10 and Comparative Examples 1 and 2 A pattern was formed using each self-assembling composition for pattern formation in the same manner as in Example 1 except that the self-assembling composition for pattern formation and the organic solvent were changed as shown in Table 5.
  • the present invention can provide a pattern forming method capable of reducing the occurrence of development defects. Therefore, the pattern forming method can be suitably used in a lithography process in manufacturing various electronic devices such as semiconductor devices and liquid crystal devices that are required to be further miniaturized.

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Abstract

La présente invention concerne un procédé de formation de motif, comprenant les étapes suivantes : une étape consistant à former un film auto-assemblé en utilisant une composition auto-assemblée pour la formation de motif et présentant une structure à séparation de phase ; et une étape consistant à retirer une phase du film auto-assemblé en utilisant un solvant organique. Le procédé de formation de motif est caractérisé en ce que le point d'ébullition du solvant organique est supérieur ou égal à 100 °C. De préférence, le solvant organique contient au moins un élément choisi à partir du groupe constitué d'hydrocarbures en C7 ou plus élevés et d'éthers en C7 ou plus élevés. En outre, la composition auto-assemblée est, de préférence, une composition contenant deux polymères, ou plus de deux polymères, ou une composition contenant un copolymère à blocs. De plus, deux étapes supplémentaires sont, de préférence, introduites avant l'étape consistant à former un film auto-assemblé : une étape consistant à former un film de sous-couche sur le substrat, et une étape consistant à former un pré-motif sur le film de sous-couche.
PCT/JP2013/058647 2012-03-30 2013-03-25 Procédé de formation de motif WO2013146715A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
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JP2015101772A (ja) * 2013-11-26 2015-06-04 東京エレクトロン株式会社 有機単分子膜の形成方法および形成装置
WO2018051907A1 (fr) * 2016-09-13 2018-03-22 日産化学工業株式会社 Composition pour la formation d'un film de recouvrement et procédé de production d'un motif par séparation de phase

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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
US20090214823A1 (en) * 2008-02-22 2009-08-27 International Business Machines Corporation Methods for aligning polymer films and related structures
JP2010122534A (ja) * 2008-11-20 2010-06-03 Jsr Corp ポジ型感光性絶縁樹脂組成物及びその硬化物
WO2012111694A1 (fr) * 2011-02-15 2012-08-23 独立行政法人理化学研究所 Procédé de production d'un substrat présentant une nanostructure superficielle
WO2013069544A1 (fr) * 2011-11-09 2013-05-16 Jsr株式会社 Composition auto-organisatrice pour la formation de motif et procédé de formation de motif

Patent Citations (5)

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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
US20090214823A1 (en) * 2008-02-22 2009-08-27 International Business Machines Corporation Methods for aligning polymer films and related structures
JP2010122534A (ja) * 2008-11-20 2010-06-03 Jsr Corp ポジ型感光性絶縁樹脂組成物及びその硬化物
WO2012111694A1 (fr) * 2011-02-15 2012-08-23 独立行政法人理化学研究所 Procédé de production d'un substrat présentant une nanostructure superficielle
WO2013069544A1 (fr) * 2011-11-09 2013-05-16 Jsr株式会社 Composition auto-organisatrice pour la formation de motif et procédé de formation de motif

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015101772A (ja) * 2013-11-26 2015-06-04 東京エレクトロン株式会社 有機単分子膜の形成方法および形成装置
WO2018051907A1 (fr) * 2016-09-13 2018-03-22 日産化学工業株式会社 Composition pour la formation d'un film de recouvrement et procédé de production d'un motif par séparation de phase
JPWO2018051907A1 (ja) * 2016-09-13 2019-06-24 日産化学株式会社 上層膜形成組成物及び相分離パターン製造方法
US10865262B2 (en) 2016-09-13 2020-12-15 Nissan Chemical Corporation Upper-layer film forming composition and method for producing a phase-separated pattern

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