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US20140314898A1 - Heat-reactive resist material, mold manufacturing method, mold, development method and pattern formation material - Google Patents

Heat-reactive resist material, mold manufacturing method, mold, development method and pattern formation material Download PDF

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US20140314898A1
US20140314898A1 US14/359,869 US201214359869A US2014314898A1 US 20140314898 A1 US20140314898 A1 US 20140314898A1 US 201214359869 A US201214359869 A US 201214359869A US 2014314898 A1 US2014314898 A1 US 2014314898A1
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heat
reactive resist
silicon
manufacturing
resist layer
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Yoshimichi Mitamura
Takuto Nakata
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Asahi Kasei Corp
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Asahi Kasei E Materials Corp
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    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/38—Treatment before imagewise removal, e.g. prebaking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/38—Moulds or cores; Details thereof or accessories therefor characterised by the material or the manufacturing process
    • B29C33/3842—Manufacturing moulds, e.g. shaping the mould surface by machining
    • B29C33/3857—Manufacturing moulds, e.g. shaping the mould surface by machining by making impressions of one or more parts of models, e.g. shaped articles and including possible subsequent assembly of the parts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
    • B29C59/022—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing characterised by the disposition or the configuration, e.g. dimensions, of the embossments or the shaping tools therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/45—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on copper oxide or solid solutions thereof with other oxides
    • 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
    • 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
    • G03F7/004—Photosensitive materials
    • G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
    • G03F7/0043—Chalcogenides; Silicon, germanium, arsenic or derivatives thereof; Metals, oxides or alloys thereof
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers
    • G03F7/322—Aqueous alkaline compositions
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/26—Apparatus or processes specially adapted for the manufacture of record carriers
    • G11B7/261—Preparing a master, e.g. exposing photoresist, electroforming
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
    • B29C59/022—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing characterised by the disposition or the configuration, e.g. dimensions, of the embossments or the shaping tools therefor
    • B29C2059/023—Microembossing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/42—Moulds or cores; Details thereof or accessories therefor characterised by the shape of the moulding surface, e.g. ribs or grooves
    • B29C33/424—Moulding surfaces provided with means for marking or patterning
    • 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
    • G03F7/0017—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor for the production of embossing, cutting or similar devices; for the production of casting means
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/12—Heads, e.g. forming of the optical beam spot or modulation of the optical beam
    • G11B7/14—Heads, e.g. forming of the optical beam spot or modulation of the optical beam specially adapted to record on, or to reproduce from, more than one track simultaneously

Definitions

  • the present invention relates to a heat-reactive resist material, mold manufacturing method, mold, development method and pattern formation material.
  • the inventors of the present invention disclosure materials with high dry etching resistance enabling the pattern size of uniform concavities and convexities, the shape of a line and the like to be controlled (for example, see Patent Document 1). Further, as a developing solution used in the exposure development process of such resist materials, the inventors of the invention disclose using amino acid, chelating agent and the like (for example, see Patent Document 2).
  • Patent Document 1 International Publication No. 2010/044400 Pamphlet
  • Patent Document 2 International Publication No. 2011/105129 Pamphlet
  • the present invention was made in view of such a respect, and it is an object of the invention to provide a heat-reactive resist material, mold manufacturing method, mold, development method and pattern formation material for enabling a fine pattern to be controlled.
  • a heat-reactive resist material of the present invention is a heat-reactive resist material containing copper oxide, and silicon or silicon oxide, and is characterized in that the content of the silicon or the silicon oxide in the heat-reactive resist material is 4.0 mol % or more less than 10.0 mol % in terms of mole or silicon.
  • a manufacturing method of a mold of the invention is manufacturing method for manufacturing a mold having a concavo-convex shape on a substrate surface using the heat-reactive resist material of the invention as described above, and is characterized by including a step (1) of forming a heat-reactive resist layer on the substrate using the heat-reactive resist material, a step (2) of exposing the heat-reactive resist layer, and then, developing with a developing solution, a step (3) of performing dry etching on the substrate with a fluorocarbon using the heat-reactive resist layer as a mask, and a step (4) of removing the heat-reactive resist layer, where the developing solution is a glycine solution or a mixed solution of glycine and ammonium oxalate.
  • a development method of the invention is a development method for developing the heat-reactive resist material of the invention as described above, and is characterized by including a step (1) of forming a heat-reactive resist layer on a substrate using the heat-reactive resist material, and a step (2) of exposing the heat-reactive resist layer, and then, developing with a developing solution, where the developing solution is glycine solution or a mixed solution of glycine and ammonium oxalate.
  • a pattern formation material of the invention is characterized by being comprised of a combination of the heat-reactive resist material of the invention as described above, and developing solution comprised of a glycine solution or mixed solution of glycine and ammonium oxalate.
  • the present invention when copper oxide is selected for a heat-reactive resist material, by adding an optimum amount of silicon or silicon oxide, it is possible to provide the heat-reactive resist material excellent in manufacturing stability such that pattern roughness (pattern fluctuations) of the resist is suppressed to be excellent and that a development difference between heated portions and unheated portions tends to occur, and to provide the mold manufacturing method using the material, mold, development method and pattern formation material.
  • FIG. 1 is a graph showing the relationship between a silicon additive amount and a particle diameter of copper oxide
  • FIG. 2 is a graph showing the relationship between a particle diameter of copper oxide and a development selection ratio relative to the silicon additive amount
  • FIG. 3 is a graph showing an intensity distribution of laser light
  • FIG. 4 is a graph showing a temperature distribution of a portion irradiated with laser light.
  • a heat-reactive resist material according to one Embodiment of the present invention is characterized by containing copper oxide, and silicon or silicon oxide, where an additive amount of silicon or silicon oxide to copper oxide is 4.0 mol % or more less than 10.0 mol % in terms of mole of silicon.
  • the copper oxide that is a component of the heat-reactive resist material changes by heat due to exposure or the like, thereby makes a development rate difference between heated portions and unheated portions by a developing solution, and enables pattern formation.
  • crystallization of copper oxide proceeds by heat due to exposure or the like, and coarse particles of copper oxide are formed.
  • the absence of coarse particles is preferable to suppress roughness of the pattern and from the excellent pattern. Further, also to make the pattern fine, the absence of coarse particles is preferable. Therefore, as a n additive to suppress crystallization of copper oxide, silicon or silicon oxide is added.
  • Silicon or silicon oxide is compatible with copper oxide little, thus enables crystallization of copper oxide to be suppressed by the pinning effect, and thereby enables formation of coarse particles to be suppressed.
  • silicon or silicon oxide is optimal.
  • copper oxide changes (decomposes) from copper (II) oxide to copper (I) oxide at high temperatures a phenomenon of reoxidation occurs in the cooling process from high temperatures to room temperature, and a part of copper (I) oxide generated by decomposition is oxidized to recover to copper (II) oxide.
  • the difference in the chemical composition becomes a little between the heated portions and the unheated portions, and the problem occurs that the development difference is a little.
  • silicon or silicon oxide to copper oxide, it is also possible to suppress reoxidation of copper (I) oxide generated by decomposition, and to prevent the development difference from decreasing.
  • the additive amount of silicon or silicon oxide required to suppress crystallization of copper oxide is 4.0 mol % or more, preferably 4.5 mol % or more, more preferably 5.5 mol % or more, and most preferably 6.5 mol % or more.
  • FIG. 1 is a graph showing the relationship between a silicon additive amount and a particle diameter of copper oxide.
  • the additive amount of silicon or silicon oxide ranging from 0 to 4 mol %, the crystal particle diameter of copper oxide decreases monotonously. Accordingly, the additive amount of silicon or silicon oxide is selected corresponding to a required pattern form. Meanwhile, in the case of adding silicon or silicon oxide in an amount of 4.0 mol % of more, since the crystal particle diameter of copper oxide does not change significantly, a large additive amount does not cause any problem, but has little effect in the viewpoint of crystal particle diameter suppression.
  • the additive amount of silicon or silicon oxide required to suppress reoxidation of copper (I) oxide is 0.01 mol % or more, preferably 0.5 mol % or more, and more preferably 1.0 mol % or more. In other words, it is possible to sufficiently exert the effect of reoxidation suppression with the additive amount of silicon or silicon oxide added to suppress crystallization.
  • the additive amount of silicon or silicon oxide is less than 10.0 mol %, preferably 9.5 mol % or less, more preferably 9.0 mol % or less, and most preferably 8.5 mol % or less.
  • FIG. 2 is a graph showing the relationship between the particle diameter of copper oxide and the development selection ratio relative to the silicon additive amount. As can be seen from FIG. 2 , there is a tendency that the selection ratio decreases when the additive amount of silicon or silicon oxide exceeds 10 mol %. Therefore, the selection ratio is preferably 5 or more, more preferably 10 or more, and most preferably 20 or more.
  • the additive amount of silicon or silicon oxide to add to copper oxide constituting the heat-reactive resist material according to this Embodiment is 4.0 mol % or more less than 10.0 mol %, preferably in the range of 4.5 mol % to 9.5 mol %, more preferably in the range of 5.5 mol % to 9.0 mol %, and most preferably in the range of 6.5 mol % to 8.5 mol %.
  • the additive amount of silicon or silicon oxide and their reasons will specifically be described below.
  • the additive amount is 4.0 mol % or more, it is possible to suppress crystallization of copper oxide and suppress reoxidation of copper (I) oxide.
  • the particle diameter of copper oxide does not change significantly in the case of adding silicon or silicon oxide in an amount of 4.0 mol % or more. Accordingly, to effectively decrease the particle diameter, it is preferable to add silicon or silicon oxide in an amount of 4.0 mol % or more.
  • the particle diameter shows the tendency that the particle diameter gently decreases with variations of some extent. It is conceivable that the variations of the particle diameter are caused by the distribution of the dispersion state of silicon or silicon oxide in copper oxide. Accordingly, a larger amount of silicon or silicon oxide is preferable in the case of intending to make the particle diameter finer or to uniform the distribution of the dispersion state of silicon or silicon oxide in copper oxide.
  • the additive amount of silicon or silicon oxide of 4.5 mol % or more is excellent in the case of intending to make the particle diameter finer or to uniform the distribution of the dispersion state of silicon or silicon oxide in copper oxide.
  • the additive amount of 5.5 mol % or more is more excellent in the case of intending to make the particle diameter finer or to uniform the distribution of the dispersion state of silicon or silicon oxide in copper oxide.
  • the additive amount when the additive amount is less than 10 mol %, it is possible to suppress the phenomenon that the development difference gradually decreases between the heated portions and the unheated portions.
  • the development selection ratio it is possible to obtain the selection ratio of 20 or more.
  • the additive amount of 9.5 mol % or less enables a higher development selection ratio of about 21 to be obtained, and is more excellent in manufacturing stability.
  • the additive amount of 9.0 mol % or less enables a higher development selection ratio of about 23 to be obtained, and is further excellent in manufacturing stability.
  • the additive amount of 8.5 mol % or less enables a higher development selection ratio of about 25 to be obtained, and is the most excellent in manufacturing stability.
  • the additive amount of silicon or silicon oxide preferably ranges from 4.0 mol % to 8.5 mol %.
  • the additive amount of silicon or silicon oxide is preferably 6.5 mol % or more less than 10.0 mol %.
  • the additive amount of silicon or silicon oxide preferably ranges from 6.5 mol % to 8.5 mol %.
  • the heat-reactive resist material of the present invention is characterized by containing copper oxide and silicon or silicon oxide i.e. containing copper oxide and silicon, or containing copper oxide and silicon oxide, and is characterized in that the oxidation degree of silicon to add is in the range of 0 to 2. Described herein is silicon with the oxidation degree lower than perfect oxide (with the degree of oxidation of 2) i.e. silicon suboxide. When the oxidation degree is near perfect oxide, silicon suboxide is capable of existing in a state where oxygen is lost from the crystalline structure of perfect oxide. However, when the oxidation degree further decreases, since it is difficult to keep the crystalline structure, generally, silicon suboxide often exists as a mixture of silicon and silicon oxide.
  • the silicon oxide of the invention includes the case where the oxidation degree is low i.e. the case of a mixture of silicon and silicon oxide. Accordingly, even in a state in which copper oxide, silicon, and silicon oxide are mixed, there is not any problem as long as the additive amount of silicon is within the above-mentioned range.
  • unit mol % representing the range of the additive amount of silicon or silicon oxide is a value expressed in percent of a value obtained by dividing the number of moles of silicon (Si) by the total number of moles of copper (Cu) and silicon (Si). Further, as the expression method other than mol %, at % exists. at % is a unit expressed in percent of the number of atoms, and in the present invention, mol % and at % express equal meaning.
  • the heat-reactive resist material according to this Embodiment it is preferable that copper oxide and a part of silicon or silicon oxide interact with each other.
  • binding energy is observed near 100.0 to 102.5 eV.
  • the observed binding energy of 2 P of Si is binding energy between silicon alone and silicon oxide alone, and therefore, the possibility of silicon suboxide is suggested.
  • SiOx (1 ⁇ X ⁇ 2) generally exists only as a gas at high temperatures, the possibility does not agree with the observation result in a thin film at room temperature. Accordingly, it is conceivable that the shift in binding energy suggests that silicon atoms have interaction with copper oxide. Accordingly, by XPS analysis, in the heat-reactive resist material according to this Embodiment, it is confirmed that copper oxide interacts with a part of silicon or silicon oxide, and it can be said that the material is preferable as a heat-reactive resist material.
  • a film thickness of a thin film comprised of the heat-reactive resist material according to this Embodiment preferably ranges from 10 nm to 50 nm. Heating of the heat-reactive resist material is achieved by the heat-reactive resist material absorbing light by exposure or the like to transform into heat. Accordingly, to achieve heating, heat-reactive resist material needs to absorb light, and this absorption amount of light is significantly dependent on the film thickness.
  • the film thickness of the thin film comprised of the heat-reactive resist material is 10 nm or more, since the light absorption amount is large, the material is easier to heat efficiently. Accordingly, the film thickness of the thin film comprised of the heat-reactive resist material of the invention is preferably 10 nm or more.
  • the film thickness is thin, it is possible to compensate for the light absorption amount by providing both upper and lower sides. Also, it is possible to compensate for the light absorption amount by providing both upper and lower sides or one of the sides of the thin film comprised of the heat-reactive resist material with a light absorption layers and the like.
  • the film thickness of the thin film comprised of the heat-reactive resist material when the film thickness of the thin film comprised of the heat-reactive resist material is 50 nm or less, it is easier to ensure uniformity in the film thickness direction by exposure. In other words, not only in the depth direction, processing accuracy of the fine pattern is also preferable in the film surface direction.
  • the film thickness of the thin film comprised of the heat-reactive resist material preferably ranges from 10 nm to 50 nm, and more preferably ranges from 20 nm to 30 nm.
  • the film thickness of the thin film comprised of the heat-reactive resist material within the most preferable range of 20 nm to 30 nm, there are advantages that the light absorption amount by exposure of the like is appropriate, and that it is possible to maintain uniformity of heat in the film thickness direction and the film depth direction, and further, there are advantages that since the rate of change in the light absorption amount is low with respect to a change in the film thickness, the unevenness of heat does not tend to occur even when the unevenness of the film thickness occurs, and that it is possible to form a uniform pattern.
  • a developing solution for the heat-reactive resist material is glycine solution or a mixed solution of glycine and ammonium oxalate.
  • the developing solution enables only heated portions to be selectively dissolved.
  • copper (II) oxide in the heat-reactive resist material are heated by exposure of the like and is thermally decomposed into copper (I) oxide.
  • the heated portions exist in a mixed state of the heated portions and the unheated portions. In other words, it is possible to selectively dissolve copper oxide with a lower valency in a state in which copper oxides with different valencies coexist.
  • Solvents used in the developing solution are not limited particularly, as long as glycine and ammonium oxalate that are components of the developing solution are dissolved suitably, and it is preferable to use water from the viewpoints of solubility, safety, versatility and cost.
  • a reaction mechanism of development proceeds by the fact that the component of the developing solution such as glycine and ammonium oxalate in the developing solution shifts to the surface of copper oxide that is the heat-reactive resist material, and subsequently develops the chelating reaction on the solid surface of copper oxide, and that the product finally eliminates.
  • the rate of the solid-liquid reaction of the copper oxide surface and the developing solution component has the most effect on selectivity, and selectivity is higher as a difference in the reaction rate in the reaction with copper oxides with different valencies is larger.
  • glycine since the reaction with copper (I) oxide is fast but the reaction with copper (II) oxide is extremely slow, it is possible to obtain excellent selectivity.
  • the chelating reaction between glycine and copper oxide is a rate-limiting reaction, the effects by the shift of the developing solution component and rate of elimination of the product are less, and it is possible to obtain high uniformity at the same time.
  • a developing solution component having high selectively and uniformity amino acids are excellent, and from the viewpoints of solubility in water, versatility, cost and the like, glycine is the most excellent.
  • the advantage of using glycine that is an amino acid there is the fact that glycine has carboxyl groups and amino groups in the same molecule, and that variations in pH are thereby small due to buttering action.
  • pH leans to the acid side of leans to the base side since copper oxide is dissolved due to the effects of acid and base, reductions in selectivity are not only derived, but it is also difficult to obtain an excellent fine pattern shape.
  • the concentration of the glycine solution that is the developing solution preferably ranges from 0.01 weight % to 10 weight %.
  • the concentration of 0.01% or more enables a desired development rate to be obtained, and is preferable in terms of productivity.
  • the concentration of 10% or more does particularly not provide a significant problem, but any remarkable change is not observed in the reaction rate when the concentration exceeds 10%, and therefore, in consideration of the cost, the concentration is preferably 10% or less.
  • a chelating agent to control the reaction rate, there are various kinds of agents, and with consideration given to high selectivity, solubility in water, versatility, cost and the like, ammonium oxalate is excellent.
  • the rate of ammonium oxalate is higher than the rate of glycine, a contribution of the reaction between ammonium oxalate and copper oxide controls the entire reaction rate, and therefore, it is preferable that the rate of glycine is higher to maintain desired selectivity.
  • the rate of ammonium oxalate is preferably in the range of 0.01 weight % to the concentration of glycine.
  • the temperature in causing the developing solution to act on the resist it is possible to change the development rate. It is possible to set the temperature arbitrarily while avoiding the ranges for causing the developing solution to freeze, boil, or evaporate at rates for remarkably changing the concentration or the component of the developing solution or the resist to decompose. In the range of high temperatures, the reaction rate is fast, the unreacted portions are easy to dissolve, and by shortening the development time as appropriate, it is possible to form a fine pattern without problems. On the other hand, in the range of low temperatures, the reaction rate is slow, the development time required to obtain a desired shape increases, and by developing for a long time, it is possible to form a fine pattern without problems.
  • the ratio has a higher value as the development temperature is lower.
  • productivity degrades.
  • the temperature preferably ranges from 10° C. to 50° C., more preferably ranges from 15° C. to 40° C., and most preferably ranges from 20° C. to 30° C. in consideration of manufacturing stability, convenience in implementing manufacturing, productivity and the like.
  • pH takes a value of approximately 1 to 11 according to glycine and ammonium oxalate to use, is desirably 3.50 or more, preferably 4.00 or more, more preferably 4.50 or more, and particularly preferably 6.00 or more.
  • pH is less than 3.50, the progression of etching is remarkable other than the complex formation reaction, and there is the case that desired selectivity is not obtained.
  • the pattern formation material of the Invention is preferably comprised of a combination of the heat-reactive resist material containing copper oxide and silicon or silicon oxide in an amount of 4.0 mol % or more less than 10.0 mol % as an additive, and the developing solution comprised of the glycine solution or the mixed solution of glycine and ammonium oxalate.
  • the heat-reactive resist material of the invention it is possible to implement both the positive type (the heated portions are dissolved in the developing solution) and the negative type (the unheated portions are dissolved in the developing solution).
  • the positive type the heated portions are decomposed, the decomposed portions are dissolved in the developing solution, and it is thereby possible to form a pattern.
  • the negative type by using crystal growth developed in applying heat to an extent that copper oxide does not decompose, it is possible to form a pattern.
  • the unheated portions in which crystal growth proceed little are dissolved in the developing solution, the heated portions in which crystal growth proceed are left due to resistance to the developing solution, and it is thereby possible to form a pattern.
  • Step (1) Form a heat-reactive resist layer on a substrate.
  • Step (2) Expose the heat-reactive resist layer, and then, develop with the developing solution comprised of the glycine solution or mixed solution of glycine and ammonium oxalate.
  • Step (3) Perform dry etching processing on the substrate with a fluorocarbon using the developed heat-reactive resist as a mask to form a fine pattern.
  • Step (4) Remove the heat-reactive resist to manufacture a mold.
  • the film of the heat-reactive resist layer preferable is film formation using a sputtering method, vapor deposition method and CVD method. Since the heat-reactive resist material allows fine pattern processing of the level of several tens of nanometers, depending on the fine pattern size, it is conceivable that the film thickness distribution and concavities and convexities on the surface of the heat-reactive resist material in film formation have extremely significant effects.
  • the heat-reactive resist material by the film formation method such as the sputtering method, vapor deposition method and CVD method rather than a film formation method such as a coating method and spray method with control of the uniformity of the film thickness being a little difficult.
  • the film formation method such as the sputtering method, vapor deposition method and CVD method
  • a film formation method such as a coating method and spray method
  • the heat release design is designed when the need arises for releasing heat from the heat-reactive resist material as rapidly as possible.
  • the heat release design is performed when the reaction by heat proceeds, by heat filling, in an area wider than the spot shape of the thermal reaction due to exposure.
  • the heat release design it is possible to adopt a laminate structure in which a film of a material with thermal conductivity higher than that of air is deposited. above the heat-reactive resist material or adopt a laminate structure in which a film of a material with thermal conductivity higher than that of the substrate is deposited below the heat-reactive resist material.
  • the development method includes an exposure step of thermally decomposing copper oxide forming the heat-reactive resist material, and a development step of supplying the developing solution to the heat-reactive resist layer and removing an oxide of copper that is thermally decomposed from the heat-reactive resist layer.
  • the thermal decomposition step by applying heat of a predetermined temperature or more to a predetermined area of the heat-reactive resist layer, an oxide of copper is thermally decomposed in the predetermined area of the heat-reactive resist layer. Further, in the thermal decomposition step, it is preferable to perform thermal decomposition of the heat-reactive resist layer by irradiating the heat-reactive resist layer with laser light.
  • the temperature of the substance also shows the same Gaussian distribution as the intensity distribution of the laser light (see FIG. 4 ).
  • the reaction proceeds only in the portion becoming the predetermined temperature or more, and it is made possible to thermally decompose the range smaller than the spot diameter of the laser light.
  • the source is not limited to laser light, as long as it is possible to decompose copper oxide with the source by applying heat of a predetermined temperature or more to a predetermined area of the heat-reactive resist layer.
  • the developing solution is supplied to the heat-reactive resist layer to dissolve and remove an oxide of copper in the predetermined area of the heat-reactive resist layer.
  • the heat-reactive resist layer subsequent to the thermal decomposition step coexist the oxide of copper that is not thermally decomposed and the oxide of copper reduced in the oxidation number by thermal decomposition.
  • Glycine and ammonium oxalate in the developing solution selectively chelation-react with the oxide of copper reduced in the oxidation number by thermal decomposition, and it is thereby possible to selectively remove the oxide of copper in the copper oxide area that is thermally decomposed from the heat-reactive resist layer.
  • the method of causing the developing solution to act on the heat-reactive resist layer is not limited particularly, and the heat-reactive resist layer may be immersed in the developing solution, or the developing solution may be sprayed onto the heat-reactive resist layer.
  • the heat-reactive resist layer may be immersed in the developing solution, or the developing solution may be sprayed onto the heat-reactive resist layer.
  • nozzle In the case of spraying the developing solution onto the heat-reactive resist layer, it is also possible to use a method of moving the nozzle, a method of rotating the heat-reactive resist layer or the like alone, and using the methods together enables development to proceed uniformly and therefore, is preferable. It is possible to use an arbitrary type of nozzle used in spray, examples thereof are a line slit, full-cone nozzle, hollow-cone nozzle, flat nozzle, uniform flat nozzle, and solid nozzle, and it is possible to select in accordance with the heat-reactive resist layer and the shape of the substrate. Further, it is possible to use a one liquid nozzle or two liquid nozzle.
  • any impurity such as insoluble fine powder exists in the developing solution there is the risk of being a cause of unevenness particularly in developing a fine pattern, and therefore, it is preferable to filter the developing solution in advance.
  • a material of a filter used filtration it is possible to select a material arbitrarily, as long as the material does not react with the developing solution, and examples thereof are PFA and PTFE.
  • the roughness of the mesh of the filter is capable of being selected corresponding to the degree of fineness of the pattern, is 0.2 ⁇ m or less, and is more preferably 0.1 ⁇ m or less.
  • spray is preferred to immersion, and furthermore, in spraying the developing solution onto the heat-reactive resist layer, it is desirable to dispose the developing solution after one-time use. In reusing the developing solution, it is preferable to remove the eluted component.
  • the development method preferably includes a step of cleaning the heat-reactive resist layer, and a step of cleaning the substrate and heat-reactive resist layer subjected to development.
  • the shape of the mold is capable of being made the shape of a plate or the shape of a sleeve (roll, drum). Many molds used in a disk of an optical disk and nanoimprint are small in the shape of a plate, and it is possible to transfer with a simplified apparatus. On the other hand, the shape of a sleeve has a property of enabling the pattern to be transferred in a large area.
  • Substrates to manufacture the mold do particularly not undergo limitations in the material.
  • preferable are materials that are excellent in surface smoothness and workability and that allow dry etching processing.
  • glass As a typical material of such materials, it is possible to use glass. Further, it is possible to use silicon, silicon dioxide or the like as the substrate. Furthermore, by providing a dry etching layer as described later, it is possible to use aluminium, titanium, copper, silver, gold or the like.
  • quartz glass is suitable as the substrate, and by controlling only the time of the dry etching processing, it is possible to form a desired aspect ratio.
  • the substrate Before manufacturing the mold, it is preferable to clean the substrate to manufacture the mold. It is possible to select a cleaning method as appropriate according to the used material and shape. For example, when the material of the substrate is glass, it is possible to clean using an alkali cleaning liquid such as inorganic alkali and organic alkali, or an acidic cleaning liquid such as hydrofluoric acid. Further, when the cleaning-targeted substance is hard to remove from the substrate or the cleaning-targeted substance removed from the substrate reattaches, it is possible to select addition of a surfactant, heating of the cleaning liquid, scrub cleaning, ultrasonic cleaning and the like as appropriate.
  • a cleaning method as appropriate according to the used material and shape. For example, when the material of the substrate is glass, it is possible to clean using an alkali cleaning liquid such as inorganic alkali and organic alkali, or an acidic cleaning liquid such as hydrofluoric acid. Further, when the cleaning-targeted substance is hard to remove from the substrate or the cleaning-targeted substance removed from the
  • IPA isopropyl alcohol
  • the substrate to manufacture the mold is in the shape of a sleeve
  • the material used in the substrate is a composite material
  • a core material is carbon-fiber reinforced plastic, and the surface is quartz glass, preferable as a cleaning agent is an alkali cleaning liquid, and preferable as a drying method is hot-water lift drying and air-knife drying.
  • an etching layer is provided between the substrate and the heat-reactive resist layer separately.
  • an etching material forming the etching layer it is preferable to select from among materials comprised of elements such that the boiling point of the primary fluoride is 250° C. or less. More specifically, preferable are materials selected from the group consisting of Ta, Mo, W, C, Si, Ge, Te, P, composites of two or more kinds thereof, oxides thereof, nitrides thereof, sulfides thereof, and carbon oxides thereof. More preferable are SiO 2 , Si and Si 3 N 4 .
  • a film thickness of the etching layer by forming the film in a thickness of a desired pattern depth, it is possible to control a processing depth of a pattern.
  • the fluorocarbons used in the dry etching processing in manufacturing the mold are not limited particularly, examples thereof include fluorocarbons such as CF 4 , CHF 3 , CH 2 F 2 , C 2 F 6 , C 3 F 8 , C 4 F 6 , C 4 F 8 , C 4 F 10 , C 5 F 10 , CCl 2 F 2 and ClF 3 , and these gases may be used alone or in combination of a plurality of gases. Further, the fluorocarbons may be mixed gases obtained by mixing O 2 , H 2 , Ar, N 2 , CO or the like into these fluorocarbons.
  • the scope of the fluorocarbons includes mixed gases of HBr, NF 3 , SF 6 , CF 3 Br, HCl, HI, BBr 3 , BCl 3 , Cl 2 and SiCl 4 , and the mixed gases mixed with gases of Ar, O 2 , H 2 , N 2 , CO and the like
  • An apparatus used in the step of performing the dry etching processing is not limited particularly, as long as the apparatus is capable of introducing a fluorocarbon in a vacuum, forming plasma and performing the etching processing, and it is possible to use commercially available dry etching apparatuses, RIE apparatuses, and ICP apparatuses. It is possible to determine the species of gas, time, power and the like to perform the dry etching processing as appropriate corresponding to the type of the resist material, type of the etching layer, thickness of the etching layer, etching rate of the etching layer and the like.
  • the method of removing the heat-reactive resist material is not limited particularly unless the substrate and etching layer are affected, and for example, it is possible to use wet etching and dry etching.
  • the heat-reactive resist material in the case of using quartz glass for the substrate to manufacture the mold, by using a general acid, it is possible to remove the heat-reactive resist material with ease by wet etching. More specifically, examples of the acid are hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid.
  • a method of causing the acid to act on the heat-reactive resist material is not limited particularly, and it is possible to use the same method as the method of causing the developing solution to act as described previously without problems.
  • the step of cleaning the substrate after removing the heat-reactive resist material is preferable to include the step of cleaning the substrate after removing the heat-reactive resist material.
  • excimer lasers such KrF and ArF lasers, semiconductor lasers, electron beam and X-ray.
  • the excimer lasers such as KrF and ArF lasers are very large-size expensive apparatuses, electron bean and X-ray require using a vacuum chamber, and there are significant limitations from the viewpoints of cost and large size. Accordingly, it is preferable to use semiconductor lasers that enable the light-source apparatus to be extremely small-size and that are inexpensive.
  • the present invention by using the methods of manufacturing a mold, it is possible to manufacture a mold having a fine pattern in the range of 1 nm to 1 ⁇ m.
  • LER Line Edge Roughness
  • SEM Scanning Electron Microscope
  • the heat-reactive resist layers deposited as described above were developed on the following conditions.
  • Example 1 a groove-shaped pattern was used as a pattern shape. It is possible to prepare various shapes and patterns by modulating the intensity of the laser during development. In the experiments, to check exposure accuracy, consecutive groove shapes and isolated circular shapes were used as a pattern.
  • the shape to form may be an elliptical shape according to the intended use, and the present invention does not undergo any limitation by the exposure shape.
  • each of the heat-reactive resist layers exposed by the above-mentioned exposure apparatus was developed.
  • the developing solution was made on the conditions as shown in Table 1.
  • “mixed solution” represents a mixed aqueous solution of glycine and ammonium oxalate.
  • “0.3+0.3” represents that 0.3 wt % of glycine and 0.3 wt % of ammonium oxalate were mixed.
  • the selection ratio in this case was 25, and thus extremely high.
  • etching of the quartz glass substrates was performed by the dry etching processing. Dry etching was carried out using SF 6 as an etching gas on the conditions that the processing gas pressure was 5 Pa, processing power was 300 W, and that the processing time was 10 minutes.
  • the etching layer depth (nm) as shown in Table 1 was observed, the etching layer reflected the width shape of the mask, and the groove-shaped pattern was formed.
  • the surface shape was transferred to a film using a UV curable resin, and an almost mold-inversed shape was transferred onto the film.
  • molds were manufactured on the same conditions as in Example 1 except that the silicon amount added to the heat-reactive resist material was 2.0 mol % or 20.0 mol %.
  • the surface shapes of the obtained molds were observed by SEM.
  • the silicon amount to add was 2.0 mol % and small (Sample 2-a)
  • LER was 5 nm
  • crystal growth of copper oxide was not suppressed much
  • roughness of the groove-shaped pattern was poorer than in Example 1 with large Si additive amounts.
  • the silicon amount to add was 20.0 mol % and large (Sample 2-b)
  • the selection ratio was 2 and low, the development difference between the exposed portion and the unexposed portion was small in development, and the Sample lacked stability in manufacturing.
  • Example 1 By comparing Example 1 with Comparative Example 1, it is understood that it is possible to form a pattern with stability in manufacturing by using the heat-reactive resist materials and developing solution according to Example 1.
  • the heat-reactive resist layers deposited as described above were developed on the following conditions.
  • Example 2 a circular pattern was used as a pattern shape.
  • each of the heat-reactive resists exposed by the above-mentioned exposure apparatus was developed.
  • the developing solution was made on the conditions as shown in Table 1. As the development time, to ensure manufacturing stability, development was carried out for 5 minutes.
  • etching of the quartz glass rolls was performed by the dry etching processing. Dry etching was carried out using SF 6 as an etching gas on the conditions that the processing gas pressure was 3 Pa, processing power was 1000 W, and that the processing time was 5 minutes.
  • the surface shape was transferred to a film using a UV curable resin, and when the surface shape and cross-sectional shape were observed by SEM, the opening width (nm) and etching layer depth (nm) as shown in Table 1 were observed.
  • molds were manufactured on the same conditions as in Sample 1-d of Example 1 except that the film thickness of the heat-reactive resist material was 5 nm (Sample 4-a) or 120 nm (Sample 4-b) and that a circular pattern was used.
  • the surface shapes of the obtained molds were observed by SEM, and when the film thickness was 5 nm and then (Sample 4-a), by increasing exposure laser power, it was possible to form an isolated circular pattern.
  • the film thickness was 120 nm and thick (Sample 4-b)
  • diffusion of heat was large in the film surface direction, it was possible to form an isolated circular pattern with a large opening width.
  • Example 2 By comparing Example 2 with Example 3, it is understood that it is possible to form a pattern with more stability in manufacturing due to the film thickness of the heat-reactive resist layer according to Example 3.
  • a mold was manufactured on the same conditions as in Sample 1-b of Example 1 except that the type of the developing solution was a glycine aqueous solution and that a circular pattern was used (Sample 5).
  • the opening width (nm) as shown in Table 1 was formed as an isolated circular pattern.
  • mold was manufactured on the same conditions as in Sample 1-d of Example 1 except that the concentration of the developing solution was 0.001% and that the development time was 10 minutes (Sample 7).
  • the surface shape of the obtained mold was observed by SEM, the portion in which the resist layer was dissolved did not reach the substrate side, and it is possible to form a pattern by further extending the time.
  • molds were manufactured on the same conditions as in Sample 1-b of Example 1 except that the development time was 5 minutes, 7 minutes or 10 minutes and that a circular pattern was used (Sample 8-a to 8-c).
  • the opening width (nm) as shown in Table 1 was formed as an isolated circular pattern. Patterns of excellent shapes were obtained in respective samples.
  • molds were manufactured on the same conditions as in Sample 1-b of Example 1 except that the temperature of the developing solution was 15° C., 30° C. or 40° C. and that a circular pattern was used (Samples 9-a to 9-c).
  • the opening width (nm) as shown in Table 1 was formed as an isolated circular pattern.
  • a mold was manufactured on the same conditions as in Sample 1-b of Example 1 except that the temperature of the developing solution was 50° C., the development time was 1 minute and that a circular pattern was used (Sample 9-d).
  • the opening width (nm) as shown in Table 1 was formed as an isolated circular pattern.
  • the selection ratios in this case were respectively 27 (Sample 9-a, 15° C.), 20 (Sample 9-b, 30° C.), 10 (Sample 9-c, 40° C.) and 5 (Sample 9-d, 50° C.), and were thus high.
  • mold was manufactured on the same conditions as in Sample 1-b of Example 1 except that the temperature of the developing solution was 60° C., the development time was 1 minute and that a circular pattern was used (Sample 10).
  • the surface shape of the obtained mold was observed by SEM, most of the resist layer was dissolved, and by further shortening the development time to 0.5 minute, it is possible to form a pattern.
  • the selection ratio in this case was measure by shortening the development time separately, and was 1.5.
  • Example 8 By comparing Example 8 with Example 9, according to the temperatures of the developing solutions according to Example 8, it is understood that it is possible to form a pattern with more stability in manufacturing.
  • mold was manufactured on the same conditions as in Sample 1-b of Example 1 except that the composition of the developing solution was changed, the development time was 2 minutes and that a circular pattern was used (Sample 11).
  • the solution species A of the developing solution in Table 1 were comprised of glycine, fluorinated ammonium, 1-hydroxy ethylidene-1, 1-diphosphonic acid and phosphonic acid, and as solvents, propylen glycol monomethyl ether and water.
  • concentration B As the concentration B, glycine was 0.9 wt %, fluorinated ammonium was 0.04 wt %, 1-hydroxy ethylidene-1, 1-diphosphonic acid was 0.06 wt % and phosphonic acid was 0.004 wt %, and pH was 2.6.
  • molds were manufactured on the same conditions as in Sample 1-b of Example 1 except that the silicon amount added to the heat-reactive resist material was 4.0 mol % (Sample 12-a), 9.0 mol % (Sample 12-b) or 9.5 mol % (Sample 12-c) and that a circular pattern was used.
  • the surface shape of each of the obtained molds was observed by SEM, and when the silicon amount to add was 4.0 mol %, LER was 4 nm.
  • the silicon amount to add was 9.0 mol % or 9.5 mol %, the development selection ratio was 23 or 21, respectively.
  • pattern roughness of the resist is excellent, the development difference between the heated portion and the unheated portion is large to enable a fine pattern to be formed with stability, and it is thereby possible to perform stable manufacturing.

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