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WO2014077215A1 - Procédé de fabrication de composé de mayénite conducteur de façon électrique - Google Patents

Procédé de fabrication de composé de mayénite conducteur de façon électrique Download PDF

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Publication number
WO2014077215A1
WO2014077215A1 PCT/JP2013/080446 JP2013080446W WO2014077215A1 WO 2014077215 A1 WO2014077215 A1 WO 2014077215A1 JP 2013080446 W JP2013080446 W JP 2013080446W WO 2014077215 A1 WO2014077215 A1 WO 2014077215A1
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Prior art keywords
mayenite compound
calcium
powder
aluminum
electron density
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Japanese (ja)
Inventor
伊藤　和弘
暁 渡邉
俊成 渡邉
宮川　直通
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AGC Inc
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Asahi Glass Co Ltd
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    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/16—Preparation of alkaline-earth metal aluminates or magnesium aluminates; Aluminium oxide or hydroxide therefrom
    • C01F7/164—Calcium aluminates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
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    • 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
    • C04B35/44—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 aluminates
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
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    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/444—Halide containing anions, e.g. bromide, iodate, chlorite
    • C04B2235/445—Fluoride containing anions, e.g. fluosilicate
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
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    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/658—Atmosphere during thermal treatment
    • C04B2235/6587—Influencing the atmosphere by vaporising a solid material, e.g. by using a burying of sacrificial powder
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    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
    • C04B2235/661—Multi-step sintering
    • C04B2235/662—Annealing after sintering
    • C04B2235/664—Reductive annealing
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    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/77—Density

Definitions

  • the present invention relates to a method for producing a conductive mayenite compound.
  • the mayenite compound has a typical crystal structure having a representative composition represented by 12CaO.7Al 2 O 3 and having three-dimensionally connected voids (cages) having a diameter of about 0.4 nm.
  • the skeleton constituting this cage is positively charged and forms 12 cages per unit cell. Since 1/6 of this cage satisfies the electrical neutrality condition of the crystal, the inside is occupied by oxygen ions. However, the oxygen ions in the cage have characteristics that are chemically different from other oxygen ions constituting the skeleton, and thus the oxygen ions in the cage are particularly called free oxygen ions. .
  • the mayenite compound is also expressed as [Ca 24 Al 28 O 64 ] 4 + ⁇ 2O 2 ⁇ .
  • Such a conductive mayenite compound is particularly referred to as a “conductive mayenite compound”.
  • Such a conductive mayenite compound can be produced, for example, by a method (Patent Document 2) in which a powder of mayenite compound is put in a carbon container with a lid and heat-treated at 1300 ° C. in a nitrogen gas atmosphere.
  • Patent Document 2 a method in which a powder of mayenite compound is put in a carbon container with a lid and heat-treated at 1300 ° C. in a nitrogen gas atmosphere.
  • this method is referred to as Conventional Method 1.
  • the conductive mayenite compound can be produced by a method (Patent Document 2) in which an object to be treated composed of a mayenite compound is placed in an alumina container with a lid together with aluminum metal and heat-treated at 1300 ° C. in a vacuum.
  • Patent Document 2 a method in which an object to be treated composed of a mayenite compound is placed in an alumina container with a lid together with aluminum metal and heat-treated at 1300 ° C. in a vacuum.
  • this method is referred to as Conventional Method 2.
  • the above-described conventional method 1 has a problem that it is difficult to obtain a conductive mayenite compound having a sufficiently high electron density.
  • the electron density of the obtained conductive mayenite compound is less than 3 ⁇ 10 20 cm ⁇ 3 .
  • the electron density of the target conductive mayenite compound is correlated with the electron density of the thin film to be formed.
  • the present inventors have discovered. In order to increase the electron density of the thin film, it is necessary to further increase the electron density of the target conductive mayenite compound.
  • the melting point of metal aluminum is 660 ° C.
  • the metal aluminum fixed matter produced by the solidification of the liquid is fixed on the surface of the produced conductive mayenite compound.
  • Such a fixed substance is firmly adhered to the conductive mayenite compound, and it is not easy to peel or remove the fixed substance.
  • the container used for the heat treatment is broken with a hammer, and the aluminum fixed around the conductive mayenite compound is further removed using an electric saw, a ceramic leuter, and a sandpaper.
  • the conductive mayenite compound As a use of the conductive mayenite compound, for example, when a relatively large product such as a target for film formation by vapor deposition is assumed, the conductive mayenite compound can be easily collected from a container or the like used for heat treatment. Is extremely unrealistic. Therefore, when such a phenomenon occurs, an additional treatment step is required when recovering the conductive mayenite compound, resulting in a problem that productivity is lowered.
  • the present invention has been made in view of such problems, and an object of the present invention is to provide a method for efficiently producing a conductive mayenite compound having a high electron density.
  • a method for producing a conductive mayenite compound (A) a step of preparing an object to be processed, wherein the object to be processed includes a mayenite compound or a precursor of a mayenite compound; (B) a step of heat-treating the object to be treated in an environment of a reducing atmosphere, In the environment, composite materials and / or alloys exist, The object to be treated is disposed in a state where it does not contact the composite material and / or alloy, The composite material and / or alloy includes calcium (Ca), magnesium (Mg), lithium (Li), aluminum (Al), silicon (Si), titanium (Ti), vanadium (V), manganese (Mn), chromium A process comprising at least one element selected from the group consisting of (Cr), sodium (Na), and gallium (Ga); The manufacturing method characterized by having is provided.
  • the composite material and / or alloy may contain calcium (Ca), aluminum (Al), or magnesium (Mg).
  • a CO source may exist in the environment.
  • the step (b) may be performed in a state where the object to be processed and the composite material and / or alloy are placed in a container containing carbon.
  • the object to be processed is A molded body containing a powder of a mayenite compound, A sintered body containing a mayenite compound, and a molded body containing calcined powder, May be selected from the group consisting of
  • a conductive mayenite compound having an electron density of 3 ⁇ 10 20 cm ⁇ 3 or more may be obtained after the step (b).
  • the said to-be-processed object contains a fluorine (F) component
  • a conductive mayenite compound containing fluorine may be obtained.
  • the present invention provides a method for producing a film-forming target containing a conductive mayenite compound using the method for producing a conductive mayenite compound having the above-described characteristics.
  • a method for producing a conductive mayenite compound (A) a step of preparing an object to be processed, wherein the object to be processed includes a mayenite compound or a precursor of a mayenite compound; (B) a step of heat-treating the object to be treated in an environment of a reducing atmosphere, In the environment, composite materials and / or alloys exist, The object to be treated is disposed in a state where it does not contact the composite material and / or alloy, The composite material and / or alloy includes calcium (Ca), magnesium (Mg), lithium (Li), aluminum (Al), silicon (Si), titanium (Ti), vanadium (V), manganese (Mn), chromium A process comprising at least one element selected from the group consisting of (Cr), sodium (Na), and gallium (Ga); The manufacturing method characterized by having is provided.
  • C12A7 mayenite compound
  • a compound having the same crystal structure as C12A7 (same type compound). Means.
  • An equivalent isomorphous compound of C12A7 is 12SrO ⁇ 7Al 2 O 3 .
  • the “conductive mayenite compound” means an electron density of 1.0 ⁇ 10 18 cm ⁇ 3 or more in which a part or all of “free oxygen ions” contained in the cage is replaced with electrons. It means mayenite compound.
  • a mayenite compound having an electron density of 3.0 ⁇ 10 20 cm ⁇ 3 or more is particularly referred to as a “high electron density conductive mayenite compound”. The electron density when all the free oxygen ions are replaced with electrons is about 2.3 ⁇ 10 21 cm ⁇ 3 .
  • the “mayenite compound” includes a “conductive mayenite compound”, a “conductive mayenite compound having a high electron density”, and a “non-conductive mayenite compound”.
  • the electron density of the produced “conductive mayenite compound” is 3.0 ⁇ 10 20 cm ⁇ 3 or more, and the electron density is significantly higher than that of the conventional method using a carbon container with a lid.
  • the “high electron density conductive mayenite compound” can be obtained.
  • the electron density of the conductive mayenite compound produced in the present invention is preferably 5.0 ⁇ 10 20 cm ⁇ 3 or more, more preferably 7.0 ⁇ 10 20 cm ⁇ 3 or more. More preferably, it is 0 ⁇ 10 21 cm ⁇ 3 or more.
  • the electron density of the conductive mayenite compound is measured by two methods according to the electron density of the mayenite compound.
  • the electron density is 1.0 ⁇ 10 18 cm ⁇ 3 to less than 3.0 ⁇ 10 20 cm ⁇ 3
  • the diffuse reflection of the conductive mayenite compound powder is measured, and the absorption spectrum obtained by Kubelka-Munk conversion is 2.8 eV ( It is calculated from the absorbance (wavelength conversion value) at a wavelength of 443 nm.
  • This method utilizes the fact that the electron density and the Kubelka-Munk conversion value are in a proportional relationship.
  • a method for creating a calibration curve will be described.
  • ESR electron spin resonance
  • the electron density is 3.0 ⁇ 10 20 cm ⁇ 3 to 2.3 ⁇ 10 21 cm ⁇ 3
  • the electron density is determined by measuring the diffuse reflection of the conductive mayenite compound powder and measuring the peak of the absorption spectrum obtained by Kubelka-Munk conversion. Converted from wavelength (energy).
  • n represents the electron density (cm ⁇ 3 )
  • E sp represents the peak energy (eV) of the absorption spectrum obtained by Kubelka-Munk transformation.
  • the conductive mayenite compound is calcium (Ca), aluminum (Al) and oxygen (O) as long as it has a C12A7 crystal structure composed of calcium (Ca), aluminum (Al) and oxygen (O).
  • a part of at least one atom selected from among the above may be substituted with another atom or atomic group.
  • a part of calcium (Ca) is magnesium (Mg), strontium (Sr), barium (Ba), lithium (Li), sodium (Na), chromium (Cr), manganese (Mn), cerium (Ce).
  • Cobalt (Co), nickel (Ni) and copper (Cu) may be substituted with one or more atoms selected from the group consisting of.
  • a part of aluminum (Al) is silicon (Si), germanium (Ge), boron (B), gallium (Ga), titanium (Ti), manganese (Mn), iron (Fe), cerium (Ce).
  • Praseodymium (Pr), scandium (Sc), lanthanum (La), yttrium (Y), europium (Eu), yttrium (Yb), cobalt (Co), nickel (Ni) and terbium (Tb) May be substituted with one or more atoms. Further, the oxygen in the cage skeleton may be substituted with nitrogen (N) or the like.
  • the conductive mayenite compound is such that at least a part of free oxygen ions in the cage is H ⁇ , H 2 ⁇ , H 2 ⁇ , O ⁇ , O 2 ⁇ , OH ⁇ , F ⁇ , Cl ⁇ , and S 2. It may be substituted with an anion such as 2- or an anion of nitrogen (N).
  • the ratio of calcium (Ca) to aluminum (Al) in the conductive mayenite compound in the present invention is a molar ratio converted to CaO: Al 2 O 3 , for example, in the range of 10: 9 to 13: 6.
  • the range is preferably 5: 8.5 to 12.6: 6.4, more preferably 11: 8 to 12.5: 6.5, and 11.5: 7.5 to 12.3: 6.7. More preferred is a range of 11.7: 7.3 to 12.25: 6.75, especially a range of 11.8: 7.2 to 12.2: 6.8, eg about 12: 7. Is particularly preferred.
  • the number of moles of calcium and other atoms is regarded as the number of moles of calcium.
  • the number of moles of aluminum and the other atoms is regarded as the number of moles of aluminum.
  • the metal aluminum adhering matter generated by solidification of the liquid adheres to the surface of the conductive mayenite compound to be produced.
  • a fixed substance is firmly adhered to the conductive mayenite compound, and it is not easy to peel or remove the fixed substance.
  • the conductive mayenite compound can be applied to a relatively large product such as a film-forming target.
  • the conductive mayenite compound is reduced from the surface of the conductive mayenite compound. It is practically very difficult to remove all the sticking material at a cost. For this reason, the conventional method 2 has a problem in terms of productivity.
  • the object to be treated is arranged in a state where it is not in direct contact with the composite material and / or alloy functioning as a reducing agent.
  • the manufacturing method according to the present invention it is significantly avoided that a fixed object such as metallic aluminum is fixed to the surface of the produced conductive mayenite compound. Therefore, in the production method of the present invention, the conductive mayenite compound produced after the heat treatment can be easily recovered.
  • the composite material and / or alloy used in the production method according to the present invention includes calcium (Ca), magnesium (Mg), lithium (Li), aluminum (Al), silicon (Si), titanium (Ti), and vanadium. It contains at least one element selected from the group consisting of (V), manganese (Mn), chromium (Cr), sodium (Na), and gallium (Ga).
  • each of these elements thermodynamically belongs to the oxide stable side (lower side in the Ellingham diagram) than the mayenite compound, and can function as a reducing agent for the mayenite compound. Therefore, the mayenite compound is reduced by heat-treating the object to be treated in the presence of such a composite material and / or alloy, and thus a “high electron density conductive mayenite compound” can be produced.
  • the electron density of the conductive mayenite compound to be manufactured is 3.0 ⁇ 10 20 cm ⁇ 3 or more, compared to a method using a carbon container with a lid like the conventional method 1.
  • a “high electron density conductive mayenite compound” having a significantly large electron density can be obtained.
  • FIG. 1 shows a method for producing a conductive mayenite compound according to an embodiment of the present invention.
  • a manufacturing method is as follows.
  • the composite material and / or alloy includes calcium (Ca), magnesium (Mg), lithium (Li), aluminum (Al), silicon (Si), titanium (Ti), vanadium (V), manganese (Mn), chromium
  • a process comprising at least one element selected from the group consisting of (Cr), sodium (Na), and gallium (Ga);
  • the object to be treated includes a mayenite compound or a precursor of a mayenite compound.
  • the object to be processed is (I) a compact of a powder of mayenite compound, It may be a sintered body of (ii) mayenite compound, or (iii) a compact of calcined powder.
  • the raw material powder is prepared such that the ratio of calcium (Ca) to aluminum (Al) is in the range of 10: 9 to 13: 6 in terms of a molar ratio converted to CaO: Al 2 O 3 .
  • CaO: Al 2 O 3 (molar ratio) is preferably in the range of 11: 8 to 12.5: 6.5, more preferably in the range of 11.5: 7.5 to 12.3: 6.7, 11
  • the range of .8: 7.2 to 12.2: 6.8 is more preferred, and about 12: 7 is particularly preferred.
  • the compound used for the raw material powder is not particularly limited as long as the ratio is maintained.
  • the raw material powder preferably contains calcium aluminate or at least two selected from the group consisting of calcium compounds, aluminum compounds, and calcium aluminates.
  • the raw material powder may be, for example, the following mixed powder: mixed powder containing calcium compound and aluminum compound, mixed powder containing calcium compound and calcium aluminate, mixed powder containing aluminum compound and calcium aluminate , Mixed powder containing calcium compound, aluminum compound and calcium aluminate, mixed powder containing only calcium aluminate.
  • Examples of calcium compounds include calcium carbonate, calcium oxide, calcium hydroxide, calcium hydrogen carbonate, calcium sulfate, calcium metaphosphate, calcium oxalate, calcium acetate, calcium nitrate, and calcium halide. Of these, calcium carbonate, calcium oxide, and calcium hydroxide are preferred.
  • Examples of the aluminum compound include aluminum hydroxide, aluminum oxide, aluminum sulfate, aluminum nitrate, and aluminum halide. Of these, aluminum hydroxide and aluminum oxide are preferred.
  • Examples of aluminum oxide (alumina) include ⁇ -alumina, ⁇ -alumina, and ⁇ -alumina, with ⁇ -aluminum oxide (alumina) being preferred.
  • CaO ⁇ Al 2 O 3 , 3CaO ⁇ Al 2 O 3 , 5CaO ⁇ 3Al 2 O 3 , CaO ⁇ 2Al 2 O 3 , CaO ⁇ 6Al 2 O 3 and the like are preferable.
  • C12A7 may be used by mixing with a calcium compound or an aluminum compound.
  • the raw material powder may further contain a fluorine (F) component.
  • a fluorine (F) component examples include calcium fluoride (CaF 2 ).
  • a fluorine (F) component is added to the raw material powder, a high electron density conductive mayenite compound in which fluorine ions are introduced into the cage can be finally produced (after step S120).
  • the raw material powder containing the fluorine (F) component is not limited to this, but may be prepared, for example, by adding calcium fluoride to the mixed powder of the calcium compound and the aluminum compound as described above.
  • the content of fluorine (F) in the raw material powder is not particularly limited.
  • the fluorine (F) content is, for example, the chemical formula of the finally obtained conductive mayenite compound.
  • the range of x may be selected to be in the range of 0 to 0.60.
  • the raw material powder prepared as described above is kept at a high temperature to synthesize a mayenite compound.
  • Synthesis may be performed under an inert gas atmosphere or under vacuum, but is preferably performed under air.
  • the synthesis temperature is not particularly limited, but is, for example, in the range of 1150 ° C to 1460 ° C, preferably in the range of 1200 ° C to 1415 ° C, more preferably in the range of 1250 ° C to 1400 ° C, and in the range of 1300 ° C to 1350 ° C. Is more preferable.
  • a mayenite compound containing a large amount of C12A7 crystal structure is easily obtained. If the synthesis temperature is too low, the C12A7 crystal structure may be reduced. On the other hand, if the synthesis temperature is too high, since the melting point of the mayenite compound is exceeded, the crystal structure of C12A7 may be reduced.
  • the synthesis temperature of the mayenite compound containing no fluorine is more preferably 1230 ° C. to 1415 ° C., further preferably 1250 ° C. to 1380 ° C., and particularly preferably 1280 ° C. to 1350 ° C.
  • the synthesis temperature of the mayenite compound containing fluorine is more preferably 1180 ° C. to 1420 ° C., further preferably 1200 ° C. to 1400 ° C., and particularly preferably 1230 ° C. to 1380 ° C.
  • the mayenite compound containing fluorine is easy to manufacture because the melting point of the compound is high and the synthesis temperature range is wide.
  • the holding time at high temperature is not particularly limited, and it varies depending on the amount of synthesis and the holding temperature.
  • the holding time is, for example, 1 hour to 12 hours.
  • the holding time is, for example, preferably 2 hours to 10 hours, and more preferably 4 hours to 8 hours.
  • the mayenite compound obtained by synthesis is a lump that is partially or entirely sintered.
  • the massive mayenite compound is pulverized to a size of, for example, about 5 mm by a stamp mill or the like. Further, pulverization is performed with an automatic mortar or a dry ball mill until the average particle size is about 10 ⁇ m to 100 ⁇ m.
  • average particle diameter means a value obtained by measurement by a laser diffraction scattering method.
  • the average particle diameter of the powder means a value measured by the same method.
  • an alcohol represented by C n H 2n + 1 OH (n is an integer of 3 or more) (for example, a wet ball mill using a isopropyl alcohol as a solvent, or a circulating bead mill)
  • n is an integer of 3 or more
  • a wet ball mill using a isopropyl alcohol as a solvent, or a circulating bead mill can be used to reduce the average particle size of the powder to 0.5 ⁇ m to 50 ⁇ m.
  • the powder of mayenite compound is prepared by the above process.
  • the mayenite compound prepared as a powder may be a conductive mayenite compound. This is because the conductive mayenite compound is more pulverizable than the non-conductive compound.
  • the method for synthesizing the conductive mayenite compound is not particularly limited, and the following method is exemplified.
  • a method in which a mayenite compound is put in a carbon container with a lid and heat-treated at 1600 ° C. International Publication No. 2005/000741
  • a mayenite compound is put in a carbon container with a lid and heat-treated in nitrogen at 1300 ° C.
  • Patent Publication No. 2006/129694 powder made of calcium carbonate powder and aluminum oxide powder, such as calcium aluminate, is put in a carbon crucible with a lid and heat treated at 1300 ° C. in nitrogen Method
  • the method for pulverizing the conductive mayenite compound is the same as the method for pulverizing the mayenite compound.
  • the conductive mayenite compound powder is prepared. Note that a mixed powder of a non-conductive mayenite compound and a conductive mayenite compound may be used.
  • the molded body may be prepared by pressure molding of a molding material made of powder or a kneaded product containing powder.
  • a molded body can be obtained by press molding, sheet molding, extrusion molding, or injection molding of the molding material.
  • the shape of the molded body is not particularly limited.
  • the raw material powder is held at a high temperature to synthesize the mayenite compound.
  • the massive mayenite compound obtained after the synthesis may be used as it is as a sintered body for the object to be processed.
  • a sintered body obtained by heat-treating the molded body shown in the column “(Preparation of molded body of mayenite compound powder)” in “(i) Method for preparing molded body of mayenite compound powder” is treated. It may be used as a body.
  • the heat treatment condition is not particularly limited as long as the compact is sintered.
  • the heat treatment may be performed in the temperature range of 300 ° C. to 1450 ° C., for example, in the atmosphere. If it is 300 ° C. or higher, the organic components are volatilized and the number of powder contacts increases, so that the sintering process is likely to proceed. If it is 1450 ° C. or lower, the shape of the sintered body is easily maintained.
  • the maximum temperature of the heat treatment is in the range of approximately 1000 ° C. to 1420 ° C., preferably 1050 ° C. to 1415 ° C., more preferably 1100 ° C. to 1380 ° C., and particularly preferably 1250 ° C. to 1350 ° C.
  • the holding time at the maximum temperature of the heat treatment is in the range of about 1 hour to 50 hours, preferably 2 hours to 40 hours, more preferably 3 hours to 30 hours. Further, even if the holding time is increased, there is no particular problem in terms of characteristics, but the holding time is preferably within 48 hours in view of manufacturing cost. You may implement in inert gas, such as argon, helium, neon, nitrogen, oxygen gas, or these mixed atmosphere, or in a vacuum.
  • inert gas such as argon, helium, neon, nitrogen, oxygen gas, or these mixed atmosphere, or in a vacuum.
  • a sintered body of the mayenite compound may be prepared by various methods.
  • the mayenite compound contained in the sintered body may be a conductive mayenite compound or a non-conductive mayenite compound. Further, the mayenite compound contained in the sintered body may be a mayenite compound containing fluorine or a mayenite compound not containing fluorine.
  • calcined powder is a powder prepared through heat treatment, and is selected from (i) calcium oxide, aluminum oxide, and calcium aluminate. Or (ii) a mixed powder of two or more kinds of calcium aluminate.
  • Examples of calcium aluminate include CaO ⁇ Al 2 O 3 , 3CaO ⁇ Al 2 O 3 , 5CaO ⁇ 3Al 2 O 3 , CaO ⁇ 2Al 2 O 3 , CaO ⁇ 6Al 2 O 3 , C12A7, and the like.
  • the ratio of calcium (Ca) to aluminum (Al) in the “calcined powder” is 9.5: 9.5 to 13: 6 in terms of a molar ratio converted to CaO: Al 2 O 3 .
  • the ratio of calcium (Ca) to aluminum (Al) is such that the molar ratio in terms of CaO: Al 2 O 3 is in the range of 10: 9 to 13: 6.
  • CaO: Al 2 O 3 (molar ratio) is preferably in the range of 11: 8 to 12.5: 6.5, more preferably in the range of 11.5: 7.5 to 12.3: 6.7, 11
  • the range of .8: 7.2 to 12.2: 6.8 is more preferred, and about 12: 7 is particularly preferred.
  • the calcined powder is also called a “precursor” of the mayenite compound.
  • the calcined powder can be prepared as follows.
  • raw material powder is prepared.
  • the raw material powder includes at least a raw material to be a calcium oxide source and an aluminum oxide source.
  • the raw material powder preferably contains two or more kinds of calcium aluminate, or at least two selected from the group consisting of calcium compounds, aluminum compounds, and calcium aluminates.
  • the raw material powder may be, for example, the following raw material powder: raw material powder containing calcium compound and aluminum compound, raw material powder containing calcium compound and calcium aluminate, raw material powder containing aluminum compound and calcium aluminate , Raw material powder containing calcium compound, aluminum compound and calcium aluminate, raw material powder containing only calcium aluminate.
  • the raw material powder includes at least a raw material A serving as a calcium oxide source and a raw material B serving as an aluminum oxide source.
  • Examples of the raw material A include calcium carbonate, calcium oxide, calcium hydroxide, calcium hydrogen carbonate, calcium sulfate, calcium metaphosphate, calcium oxalate, calcium acetate, calcium nitrate, and calcium halide. Of these, calcium carbonate, calcium oxide, and calcium hydroxide are preferred.
  • Examples of the raw material B include aluminum hydroxide, aluminum oxide, aluminum sulfate, aluminum nitrate, and aluminum halide. Of these, aluminum hydroxide and aluminum oxide are preferred.
  • Examples of aluminum oxide (alumina) include ⁇ -alumina, ⁇ -alumina, and ⁇ -alumina, with ⁇ -aluminum oxide (alumina) being preferred.
  • the calcined powder may contain substances other than the raw material A and the raw material B.
  • the calcined powder may contain a fluorine component or may not contain a fluorine component.
  • the raw material powder containing the raw material A and the raw material B is heat-treated. Thereby, the calcined powder containing calcium and aluminum is obtained.
  • the ratio of calcium (Ca) to aluminum (Al) in the calcined powder is in the range of about 10: 9 to 13: 6 in terms of a molar ratio converted to CaO: Al 2 O 3 .
  • the maximum temperature of the heat treatment is approximately in the range of 600 ° C to 1250 ° C, preferably 900 ° C to 1200 ° C, more preferably 1000 ° C to 1100 ° C.
  • the holding time at the maximum temperature of the heat treatment is in the range of about 1 hour to 50 hours, preferably 2 hours to 40 hours, more preferably 3 hours to 30 hours. Further, even if the holding time is lengthened, there is no particular problem in terms of characteristics, but the holding time is preferably within 48 hours in view of manufacturing cost.
  • the heat treatment may be performed in the air.
  • the heat treatment may be performed in an inert gas such as argon, helium, neon, nitrogen, an oxygen gas, an atmosphere in which these gases are mixed, or in a vacuum.
  • the calcined powder obtained after the heat treatment is usually a lump that is partially or entirely sintered. For this reason, if necessary, a pulverization treatment (coarse pulverization and / or refinement) as shown in the above-mentioned column (Preparation of mayenite compound powder) may be performed.
  • the calcined powder is prepared by the above process.
  • the formation method of the molded body is not described further here because the method similar to the method described in the above-mentioned preparation method (i) (preparation of molded body of mayenite compound powder) can be applied.
  • the object to be processed may be prepared by other methods.
  • the object to be treated may be a powder compact in which a powder of a mayenite compound and calcined powder are mixed.
  • the heat treatment of the object is performed under a “reducing atmosphere”.
  • the “reducing atmosphere” means a general name of an atmosphere having an oxygen partial pressure of 10 ⁇ 3 Pa or less in the environment, and the environment is an inert gas atmosphere or a reduced pressure environment (for example, a pressure of 100 Pa or less Vacuum environment).
  • the oxygen partial pressure is preferably 10 ⁇ 5 Pa or less, more preferably 10 ⁇ 10 Pa or less, and even more preferably 10 ⁇ 15 Pa or less.
  • the environment may contain carbon monoxide gas.
  • the carbon monoxide gas may be supplied from the outside to the environment to which the object to be treated is exposed.
  • a carbon-containing container may be used and the object to be treated may be arranged in the carbon-containing container.
  • carbon monoxide gas is supplied from the carbon-containing container during the heat treatment of the target object.
  • carbon may be added to the composite material and / or alloy described later. Or you may use the member used as another CO source.
  • the method for adjusting the environment to a reducing atmosphere during the heat treatment of the workpiece is not particularly limited.
  • the pressure is more preferably 70 Pa or less, still more preferably 40 Pa or less, still more preferably 20 Pa or less, still more preferably 10 Pa or less, and particularly preferably 1 Pa or less.
  • an inert gas atmosphere (excluding nitrogen gas) having an oxygen partial pressure of 1000 Pa or less may be supplied to the carbon-containing container.
  • the oxygen partial pressure of the inert gas atmosphere to be supplied is preferably 100 Pa or less, more preferably 10 Pa or less, still more preferably 1 Pa or less, and particularly preferably 0.1 Pa or less.
  • the inert gas atmosphere may be an argon gas atmosphere or the like.
  • the composite material and / or the alloy is disposed in the environment where the object to be treated is exposed during the heat treatment.
  • This composite material and / or alloy includes calcium (Ca), magnesium (Mg), lithium (Li), aluminum (Al), silicon (Si), titanium (Ti), vanadium (V), manganese (Mn), chromium It contains at least one element selected from the group consisting of (Cr), sodium (Na), and gallium (Ga).
  • a highly reducing substance is present in a high concentration in the heat treatment environment of the object to be treated. This is because as the reducing property of the atmosphere increases, the reduction of the object to be processed can be promoted.
  • concentration of the reducing agent in the processing environment depends on the vapor pressure of the reducing agent, and the higher the vapor pressure, the higher the concentration in the environment.
  • vapor pressure at 1200 ° C., sodium (Na), magnesium (Mg), lithium (Li), calcium (Ca), manganese (Mn), gallium (Ga), aluminum (Al), chromium (Cr). , Silicon (Si), titanium (Ti), vanadium (V) in this order. From the viewpoint of vapor pressure, sodium (Na), magnesium (Mg), lithium (Li), and calcium (Ca) are preferable.
  • magnesium (Mg), lithium (Li), and calcium (Ca) are preferable from the viewpoint of reducing power and vapor pressure.
  • magnesium (Mg) and calcium (Ca) are preferable because they are easy to handle.
  • the composite material and / or alloy used in the present invention contains such a highly reducible and high vapor pressure element, thereby accelerating the reduction reaction of the object to be processed and having a high electron density mayenite compound. Can be manufactured.
  • calcium (Ca) and aluminum (Al) are particularly preferable. This is because these elements are the same elements as the main constituent components contained in the conductive mayenite compound. That is, when the reduction reaction of the object to be processed proceeds in an environment containing these elements, it is suppressed that a part of the skeleton constituent elements of the produced conductive mayenite compound is replaced with other elements. .
  • the element contained in the composite material and / or alloy is more preferably calcium (Ca), aluminum (Al), and / or magnesium (Mg).
  • the composite material and / or the alloy may further contain subcomponents.
  • the role of the subcomponent is to adjust the activity of the main component (the main component that reduces the mayenite compound) and to improve the handling properties of the composite material and / or alloy.
  • the composite material and / or the alloy may include, for example, an alloy (solid solution, eutectic, or intermetallic compound) containing at least one of the above elements.
  • the composite material and / or alloy may include carbides, nitrides, and / or borides containing at least one of the elements.
  • the composite material and / or alloy may be in any form such as a lump, powder, plate, foil, or coarse. What is necessary is just to make it the component which reduces a mayenite compound and becomes a conductive mayenite compound vaporize from a composite material and / or an alloy, and can exist in an environment.
  • the composite material and / or alloy may be, for example, aluminum and carbide, or a calcium alloy, an aluminum alloy, and a magnesium alloy.
  • Examples of the composite material of aluminum and carbide include Alsic (AlSiC).
  • Examples of the calcium alloy include calcium silicide (CaSi 2 ) and an alloy of calcium (Ca) and magnesium (Mg).
  • Examples of the aluminum alloy include duralumin (an alloy of aluminum (Al), copper (Cu), magnesium (Mg), and manganese (Mn)).
  • Aluminum alloys are classified by numbers such as “A1085”.
  • the 1000 range indicates that the purity of aluminum is 99% or higher.
  • the 2000 series indicates that copper (Cu) is added, the 3000 series indicates that manganese (Mn) is added, and the 4000 series indicates that silicon (Si) is added.
  • the 5000 series shows that magnesium (Mg) is added.
  • the 6000 series indicates that magnesium (Mg) and silicon (Si) are added, the 7000 series indicates that zinc (Zn) and magnesium (Mg) are added, and the 8000 series is 2000 series. This shows that lithium (Li) is further added to the 5000 series or 7000 series aluminum alloy.
  • examples of the aluminum alloy include A1085, A1070, A2014, A3003, A5005, A6061, A7010, and A8021.
  • magnesium alloy examples include magnesium silicide (Mg 2 Si).
  • a magnesium alloy is represented using a material symbol of ASTM (American Society of Testing and Materials, American Material Testing Association) standard.
  • AM system alloy (alloy of magnesium (Mg) and aluminum (Al)); AZ series (magnesium (Mg), aluminum (Al) and zinc (Zn) alloy); ZK system (magnesium (Mg), zinc (Zn) and zirconia (Zr) alloy); ZC system (alloy of magnesium (Mg), copper (Cu) and zinc (Zn)); EZ type (magnesium (Mg), rare earth element and zirconia (Zr) alloy); QE system (magnesium (Mg), zirconia (Zr), rare earth element and silver (Ag) alloy); WE system (magnesium (Mg), yttria (Y) and rare earth alloy); AS system (magnesium (Mg), aluminum (Al) and silicon (Si) alloy); AE system (magnesium (Mg), aluminum (Al) and rare earth alloy); and M system (magnesium (Mg) and manganese (Mn) alloy).
  • A is aluminum (Al)
  • Z is zinc (Zn)
  • K is zirconium (Zr)
  • C is copper (Cu)
  • E is a rare earth element
  • composition of the alloy is expressed as AZ31
  • A is the element with the first addition amount
  • Z is the element with the second addition amount
  • 3 is the element with the first addition amount.
  • % By weight 1 indicates the weight% of the element with the second added amount.
  • aluminum is 3% by weight
  • zirconium is 1% by weight
  • the remainder is magnesium.
  • zinc is less than 1%.
  • Composition is representative.
  • examples of the magnesium alloy include AM20, AM50B, AM60A, AZ31, AZ61, AZ80, AS21, AS41B, and AE42.
  • calcium silicide (CaSi 2 ) which is one of calcium alloys, is particularly preferable. This is because this alloy contains calcium (Ca) which is a component of the conductive mayenite compound and has a strong reducing power. Further, silicon (Si) contained in this alloy is a safe material and is abundant. For this reason, calcium silicide (CaSi 2 ) is preferable because it is easy to handle.
  • the object to be processed is placed in the processing environment without being in contact with the composite material and / or the alloy.
  • the heat treatment temperature of the object to be treated is preferably in the range of 1080 ° C to 1450 ° C.
  • heat processing temperature is lower than 1080 degreeC, there exists a possibility that sufficient electroconductivity may not be provided to a mayenite compound.
  • the heat treatment temperature is higher than 1450 ° C., the melting point of the mayenite compound is exceeded, so that the crystal structure is decomposed and the electron density is lowered.
  • the heat treatment temperature is preferably in the range of 1180 ° C. to 1415 ° C., more preferably in the range of 1230 ° C. to 1380 ° C., further preferably in the range of 1240 ° C. to 1340 ° C., and most preferably in the range of 1250 ° C. to 1320 ° C.
  • the heat treatment temperature is preferably in the range of 1080 ° C to 1430 ° C, more preferably in the range of 1180 ° C to 1415 ° C, further preferably in the range of 1230 ° C to 1380 ° C.
  • the range of 1 ° C to 1340 ° C is more preferred, and the range of 1250 ° C to 1320 ° C is most preferred.
  • the high temperature holding time of the workpiece is usually in the range of 30 minutes to 50 hours, although it depends on the heat treatment temperature.
  • the high temperature holding time of the object to be treated is preferably in the range of 1 hour to 40 hours, more preferably in the range of 2 hours to 30 hours, further preferably in the range of 3 hours to 25 hours, and further in the range of 4 hours to 20 hours. A range of 4 to 16 hours is most preferred.
  • the retention time of the object to be processed is less than 30 minutes, there is a possibility that a conductive mayenite compound having a sufficiently high electron density may not be obtained, and sintering is insufficient. May be fragile. Further, even if the holding time is increased, there is no particular problem in terms of characteristics, but the holding time is preferably within 50 hours because the desired shape of the mayenite compound can be easily held.
  • an aluminum foil may be disposed on at least a part of the surface of the object to be processed, and aluminum derived from the aluminum foil may be brought into contact with at least a part of the surface of the object to be processed during the heat treatment.
  • the aluminum foil may or may not be in contact with the surface of the object to be processed.
  • the object to be treated is kept at a temperature in the range of 1080 ° C. to 1450 ° C., the aluminum melt derived from the aluminum foil is in a state of being in contact with the surface of the object to be treated.
  • the foil is preferably arranged.
  • the thickness of the aluminum foil is not particularly limited, but may be in the range of 5 ⁇ m to 1000 ⁇ m, for example. If the total thickness is within this range, a plurality of aluminum foils may be placed on the bottom surface of the object to be processed.
  • a conductive mayenite compound having a high electron density of 3 ⁇ 10 20 cm ⁇ 3 or more is produced.
  • the electroconductive mayenite compound of the high electron density containing a fluorine is manufactured.
  • fluorine may be introduced into the cage or may be introduced into the cage skeleton.
  • FIG. 2 schematically shows a configuration diagram of an apparatus used when the object to be processed is heat-treated.
  • the apparatus 200 includes a carbon container 210 having an open top, a carbon lid 215 disposed on the carbon container 210, an alumina container 230 with an alumina lid 235 disposed in the carbon container 210, Have
  • a partition plate 240 and a heat-resistant dish (for example, an alumina dish) 250 are disposed in the alumina container 230.
  • a heat-resistant dish for example, an alumina dish
  • a composite material and / or alloy 260 is installed, for example, in the form of a powder or a sheet.
  • the partition plate 240 is used for placing the workpiece 270 on the top.
  • the partition plate 240 is composed of an alumina plate having a large number of through holes.
  • the carbon container 210 and the carbon lid 215 serve as a supply source of carbon monoxide gas when the object to be processed 270 is heat-treated.
  • the entire apparatus 200 is accommodated in a heat-resistant airtight container, and this heat-resistant airtight container is connected to an exhaust system. For this reason, the inside of a heat resistant airtight container and also the inside of the carbon container 210 can be controlled to a desired reduced pressure (vacuum) environment.
  • a method for producing a conductive mayenite compound having a high electron density using the apparatus 200 will be described by taking as an example the case where the object to be treated 270 is formed of a compact of a mayenite compound powder.
  • the entire apparatus 200 is controlled to a predetermined reduced pressure environment.
  • the object 270 is held at a temperature of 1080 ° C. to 1450 ° C. using the apparatus 200.
  • a conductive mayenite compound having a high electron density is generated from the object 270 after the heat treatment.
  • the apparatus 200 can be used to produce a conductive mayenite compound having a high electron density.
  • the to-be-processed object 270 contains (almost) no mayenite compound.
  • the object to be treated 270 is held at a temperature of 1230 ° C. to 1415 ° C., calcium oxide, aluminum oxide, and calcium aluminate in the calcined powder react to produce a nonconductive mayenite compound.
  • While the object to be treated 270 is kept at high temperature, carbon monoxide gas is generated from the carbon container 210 and the carbon lid 215 side. Further, due to the reducing properties of the composite material and / or the alloy 260, free oxygen ions in the cage of the generated non-conductive mayenite compound are quickly replaced with electrons. Thereby, a conductive mayenite compound having a high electron density is generated. Thereafter, sintering of the generated high-electron-density conductive mayenite compound proceeds through a process similar to that of normal ceramic particles, forming a sintered body of the high-electron-density conductive mayenite compound. Is done.
  • a conductive mayenite compound having a high electron density can be generated and sintered directly from the calcined powder.
  • FIG. 2 is an example, and it will be apparent to those skilled in the art that the object to be processed may be heat-treated using another apparatus.
  • the object to be processed is arranged in a state where it is not in direct contact with the composite material and / or alloy that functions as a reducing agent. Therefore, in the manufacturing method according to an embodiment of the present invention, it is significantly avoided that a fixed object such as metal aluminum is fixed to the surface of the generated high electron density conductive mayenite compound. For this reason, in the manufacturing method by one Example of this invention, the electroconductive mayenite compound of the high electron density produced
  • a target for example, a sputtering target used when forming a film by a vapor deposition method
  • This target is composed of a conductive mayenite compound having a high electron density.
  • a film-forming target including a conductive mayenite compound having an electron density of 3 ⁇ 10 20 cm ⁇ 3 or more and a minimum dimension of 5 mm or more In the flat target of a disc, a target having a diameter of preferably 50 mm or more, more preferably 75 mm or more, still more preferably 100 mm or more, particularly preferably 200 mm or more can be produced.
  • a rectangular flat target having a major axis of preferably 50 mm or more, more preferably 75 mm or more, still more preferably 100 mm or more, particularly preferably 200 mm or more can be produced.
  • a cylinder having a height of preferably 50 mm or more, more preferably 75 mm or more, still more preferably 100 mm or more, and particularly preferably 200 mm or more can be produced.
  • the electron density and relative density of the deposition target are preferably high, and the electron density is preferably 5.0 ⁇ 10 20 cm ⁇ 3 or more, more preferably 1.0 ⁇ 10 21 cm ⁇ 3 or more, and 1.3 ⁇ 10 21 cm ⁇ 3 or more is more preferable, and 1.5 ⁇ 10 21 cm ⁇ 3 or more is particularly preferable.
  • the relative density is preferably 90% or more, more preferably 93% or more, and particularly preferably 95% or more.
  • an amorphous thin film containing electrons is formed. be able to.
  • An amorphous thin film containing electrons can be obtained when the electron density is in the range of 2 ⁇ 10 18 cm ⁇ 3 to 2.3 ⁇ 10 21 cm ⁇ 3 .
  • the amorphous thin film may be composed of an amorphous solid material containing calcium, aluminum, and oxygen.
  • amorphous oxidation containing calcium and aluminum is performed.
  • a thin film of a material electride can be formed.
  • the resulting amorphous thin film shows light absorption at a photon energy position of 4.6 eV.
  • the electron density of the obtained amorphous thin film may be 1 ⁇ 10 19 cm ⁇ 3 or more, or 1 ⁇ 10 20 cm ⁇ 3 or more.
  • the work function of the resulting amorphous thin film may be 2.8 to 3.2 eV.
  • the ratio of the light absorption coefficient at the 3.3 eV position to the light absorption coefficient at the 4.6 eV photon energy position may be 0.35 or less.
  • the F + center concentration may be less than 5 ⁇ 10 18 cm ⁇ 3 .
  • the thin film of the electron injection layer of the organic EL element can be formed using the film formation target of the present invention.
  • Examples 1 to 13 are examples, and examples 51 and 52 are comparative examples.
  • Example 1 A high electron density conductive mayenite compound was prepared by the following method.
  • this white lump was pulverized into pieces having a size of about 5 mm with an alumina stamp mill, and further coarsely pulverized with an alumina automatic mortar to obtain white particles A1.
  • the particle size of the obtained white particles A1 was measured by a laser diffraction scattering method (SALD-2100, manufactured by Shimadzu Corporation), the average particle size was 20 ⁇ m.
  • the compact C1 was heat-treated at a high temperature to produce a high electron density conductive mayenite compound.
  • the formed body C1 was processed into a shape having a length of 19 mm, a width of 8 mm, and a thickness of 5 mm, and this was used as a target object.
  • the apparatus 300 includes an alumina container 310 with an alumina lid 315, a first carbon container 330 with a carbon lid 335, and a second carbon with a carbon lid 355.
  • a container 350 a calcium silicide layer 320 configured by laying 0.5 g of calcium silicide powder (CaSi 2 , high purity chemical company, purity 99%) is disposed on the bottom of the alumina container 310.
  • the calcium silicide layer 320 becomes a calcium vapor source that generates calcium vapor when the device 300 becomes hot.
  • the alumina container 310 has a substantially cylindrical shape with an outer diameter of 40 mm, an inner diameter of 38 mm, and a height of 40 mm.
  • the first carbon container 330 has a substantially cylindrical shape with an outer diameter of 60 mm, an inner diameter of 50 mm, and a height of 60 mm, and the second carbon container 350 has an outer diameter of 80 mm, an inner diameter of 70 mm, and a height of 75 mm. It has a cylindrical shape.
  • This device 300 was used as follows.
  • the formed body C1 which is the object to be processed was placed in the alumina container 310.
  • two identically shaped alumina blocks 325 were disposed on the calcium silicide layer 320, and an alumina plate 328 having a thickness of 1 mm was disposed on the alumina block 325.
  • a lid 315 was placed on the alumina container 310. In this state, the molded body C1 is not in direct contact with the calcium silicide layer 320.
  • this apparatus 300 was installed in an electric furnace capable of adjusting the atmosphere.
  • the furnace was evacuated using a rotary pump and a mechanical booster pump. Then, after the pressure in the furnace at room temperature became 20 Pa or less, heating of the apparatus 300 was started and heated to 1300 ° C. at a temperature increase rate of 300 ° C./hour.
  • the apparatus 300 was held at 1300 ° C. for 6 hours, and then cooled to room temperature at a temperature decrease rate of 300 ° C./hour.
  • a black material D1 having a black surface was obtained.
  • the black material D1 could be easily recovered from the apparatus 300.
  • the relative density of the black material D1 was 96.7%.
  • the calcium silicide (CaSi 2 ) powder was mostly changed to silicon carbide (SiC) after the heat treatment, and almost no calcium compound was present. Therefore, the main component was reduced mayenite compound is considered to be calcium (Ca) component in the silicide calcium (CaSi 2).
  • an electron density measurement sample was collected from the black material D1.
  • a sample was obtained by roughly pulverizing the black material D1 using an automatic mortar made of alumina, and collecting the obtained coarse powder from a portion corresponding to the central portion of the black material D1.
  • the obtained sample had a dark brown color close to black.
  • this sample was found to have only a C12A7 structure.
  • the electron density determined from the peak position of the light diffuse reflection spectrum of the obtained powder was 1.6 ⁇ 10 21 cm ⁇ 3 .
  • the black material D1 is a conductive mayenite compound having a high electron density.
  • Example 2 A high electron density conductive mayenite compound was prepared in the same manner as in Example 1 above.
  • Example 2 the heat treatment temperature was 1240 ° C. in the above-described (manufacturing of the conductive mayenite compound) step. Other conditions are the same as in Example 1.
  • black material D2 a black material having a black surface
  • the black material D2 could be easily recovered.
  • the relative density of the black material D2 was 96.5%.
  • the black material D2 is a conductive mayenite compound having a high electron density.
  • Example 3 A high electron density conductive mayenite compound was prepared in the same manner as in Example 1 above.
  • Example 3 the heat treatment temperature was set to 1240 ° C. and the holding time was set to 12 hours in the above-described process (manufacturing the conductive mayenite compound). Other conditions are the same as in Example 1.
  • a black material having a black surface (hereinafter referred to as a black material “D3”) was obtained.
  • the black material D3 could be easily recovered.
  • the relative density of the black material D3 was 97.5%.
  • the black material D3 is a conductive mayenite compound having a high electron density.
  • Example 4 A high electron density conductive mayenite compound was prepared in the same manner as in Example 1 above.
  • Example 4 the heat treatment temperature was set to 1360 ° C. in the above-described (manufacture of conductive mayenite compound) step. Other conditions are the same as in Example 1.
  • black material D4 a black material having a black surface
  • the black material D4 could be easily recovered.
  • the relative density of the black material D4 was 98.0%.
  • the black material D4 had only the C12A7 structure.
  • the electron density of the black material D4 was 1.0 ⁇ 10 21 cm ⁇ 3 .
  • the black material D4 is a conductive mayenite compound having a high electron density.
  • Example 5 A high electron density conductive mayenite compound was prepared in the same manner as in Example 1 above.
  • Example 5 the sintered body E5 obtained by heat-treating the molded body C1 in the air was used as the object to be processed in the above-described process (manufacturing the conductive mayenite compound).
  • the sintered compact E5 was produced as follows. A molded body C1 having a length of 19 mm, a width of 8 mm, and a thickness of 5 mm was heated to 1300 ° C. in the atmosphere. The heating rate was 300 ° C./hour. Next, this was held at 1300 ° C. for 6 hours, and then cooled to room temperature at a temperature decrease rate of 300 ° C./hour. Thereby, the sintered compact E5 was obtained.
  • the step of (production of conductive mayenite compound) was performed in the same manner as in Example 1 except that the sintered body E5 was used as the object to be processed. As a result, a black material having a black surface (hereinafter referred to as black material “D5”) was obtained. The black material D5 could be easily recovered. The relative density of the black material D5 was 95.5%.
  • the black material D5 is a conductive mayenite compound having a high electron density.
  • Example 6 A high electron density conductive mayenite compound was prepared in the same manner as in Example 1 above.
  • Example 6 in the above-described step (manufacturing the mayenite compound compact), a conductive mayenite compound powder having an electron density of 5.0 ⁇ 10 19 cm ⁇ 3 is used instead of the white powder B1. Thus, a compact C6 was produced.
  • the conductive mayenite compound powder was prepared as follows. First, the compact C1 in Example 1 was placed in a carbon lidded container. Next, this container was heated to 1300 ° C. at a temperature rising rate of 300 ° C./hour and held at 1300 ° C. for 6 hours. The atmosphere was nitrogen. Thereafter, the container was cooled at a cooling rate of 300 ° C./hour. This obtained the black lump.
  • this black mass was pulverized by the same pulverization method used in the above-mentioned (Mayenite compound synthesis) step, and a conductive mayenite compound powder having an electron density of 5.0 ⁇ 10 19 cm ⁇ 3. Got.
  • the obtained powder was dark green and was confirmed to have a C12A7 structure.
  • the average particle size of the powder was 1.4 ⁇ m.
  • the step of (manufacture of conductive mayenite compound) was carried out in the same manner as in Example 1 except that the compact C6 composed of conductive mayenite compound powder was used as the object to be treated. As a result, a black material having a black surface (hereinafter referred to as a black material “D6”) was obtained. The black material D6 could be easily recovered. The relative density of the black material D6 was 97.0%.
  • the black material D6 is a conductive mayenite compound having a high electron density.
  • Example 7 A high electron density conductive mayenite compound was prepared in the same manner as in Example 1 above. However, in this Example 7, the following steps were carried out instead of the above-mentioned step (production of a mayenite compound molded body).
  • the molded body was cut into a rectangular parallelepiped shape having a length of 19 mm, a width of 8 mm, and a thickness of 6 mm with a commercially available cutter to obtain a molded body C7.
  • the molded body C7 was used as an object to be processed, and the above-described (manufacture of conductive mayenite compound) step was performed in the same manner as in Example 1.
  • a black material having a black surface (hereinafter referred to as a black material “D7”) was obtained.
  • the black material D7 could be easily recovered.
  • the relative density of the black material D7 was 96.8%.
  • the lattice constant of the black material D7 was smaller than the value of the black material D1 in Example 1. From this, it is considered that the mayenite compound of the black material D7 contains fluorine.
  • the black material D7 was fractured, and the composition analysis of the fracture surface was performed by energy dispersive X-ray analysis (EDX). From the analysis results, it was found that the ratio of detected fluorine was close to the mixing ratio of the mixed powder F7.
  • EDX energy dispersive X-ray analysis
  • the black substance D7 is a high electron density conductive mayenite compound containing fluorine.
  • Example 8 A high electron density conductive mayenite compound was prepared in the same manner as in Example 7 above.
  • Example 8 the heat treatment temperature was set to 1200 ° C. in the above-described process (manufacture of conductive mayenite compound). Other conditions are the same as in Example 7.
  • a black material having a black surface (hereinafter referred to as a black material “D8”) was obtained.
  • the black material D8 could be easily recovered.
  • the black material D8 had only the C12A7 structure.
  • the electron density of the black material D8 was 1.1 ⁇ 10 21 cm ⁇ 3 .
  • the relative density of the black material D8 was 95.0%.
  • the black material D8 is a high electron density conductive mayenite compound containing fluorine.
  • Example 9 A high electron density conductive mayenite compound was prepared in the same manner as in Example 1 above.
  • Example 9 in the above-described process (production of conductive mayenite compound), The pressure in the furnace at room temperature was 50 Pa. Other conditions are the same as in Example 1.
  • black material D9 a black material having a black surface
  • the black material D9 could be easily recovered.
  • the relative density of the black material D9 was 97.9%.
  • the black material D9 had only the C12A7 structure.
  • the electron density of the black material D9 was 1.0 ⁇ 10 21 cm ⁇ 3 .
  • the black material D9 is a conductive mayenite compound having a high electron density.
  • Example 10 A high electron density conductive mayenite compound was prepared in the same manner as in Example 1 above.
  • Example 10 in the above-described process (production of conductive mayenite compound), The first carbon container 330 with the carbon lid 335 and the second carbon container 350 with the carbon lid 355 were not used. That is, the object to be treated was heat-treated in an environment where no carbon was present. Other conditions are the same as in Example 1.
  • a black material having a black surface (hereinafter referred to as a black material “D10”) was obtained.
  • the black material D10 could be easily recovered.
  • the relative density of the black material D10 was 96.4%.
  • the black material D10 had only the C12A7 structure.
  • the electron density of the black material D10 was 1.0 ⁇ 10 21 cm ⁇ 3 .
  • the black material D10 is a conductive mayenite compound having a high electron density.
  • Example 11 A high electron density conductive mayenite compound was prepared in the same manner as in Example 3 above.
  • Example 11 0.5 g of magnesium silicide powder (Mg 2 Si, High Purity Chemical Co., Ltd.) was used instead of calcium silicide powder (CaSi 2 ) in the above-described step (manufacture of conductive mayenite compound). Manufactured, purity 99%). Other conditions are the same as in Example 3.
  • a black material having a black surface (hereinafter referred to as a black material “D11”) was obtained.
  • the black material D11 could be easily recovered.
  • the relative density of the black material D11 was 96.0%.
  • the black material D11 is a conductive mayenite compound having a high electron density.
  • Example 12 A high electron density conductive mayenite compound was prepared in the same manner as in Example 1 above.
  • Example 12 in the above-described process (production of conductive mayenite compound), The molded body C1 was wrapped with a commercially available aluminum foil. Specifically, four aluminum foils having a thickness of 11 ⁇ m were stacked to wrap the compact C1. Other conditions are the same as in Example 1.
  • a black material having a black surface (hereinafter referred to as a black material “D12”) was obtained.
  • the black material D12 could be easily recovered.
  • the relative density of the black material D12 was 96.0%.
  • the black material D12 had only the C12A7 structure.
  • the electron density of the black material D12 was 1.7 ⁇ 10 21 cm ⁇ 3 .
  • the black material D12 is a conductive mayenite compound having a high electron density.
  • Example 13 A high electron density conductive mayenite compound was prepared in the same manner as in Example 1 above.
  • Example 13 the apparatus 400 was used in the above-described process (manufacturing the conductive mayenite compound). Other conditions are the same as in Example 1.
  • FIG. 4 shows an apparatus used for heat treatment of the compact C1.
  • the apparatus 400 includes an alumina container 410 with an alumina lid 415, a first carbon container 430 with a carbon lid 435, and a second carbon with a carbon lid 455.
  • a container 450 is shown in FIG. 4, the apparatus 400 includes an alumina container 410 with an alumina lid 415, a first carbon container 430 with a carbon lid 435, and a second carbon with a carbon lid 455.
  • a container 450 is shown in FIG. 4, the apparatus 400 includes an alumina container 410 with an alumina lid 415, a first carbon container 430 with a carbon lid 435, and a second carbon with a carbon lid 455.
  • First and second alumina containers 420 and 460 are disposed at the bottom of the alumina container 410.
  • the first alumina container 420 0.5 g of calcium silicide powder (CaSi 2 , manufactured by Kojundo Chemical Co., Ltd., purity 99%) was disposed as the calcium silicide layer 421.
  • the second alumina container 460 1.0 g of aluminum powder (manufactured by Junsei Chemical Co., 200 mesh) was placed as the aluminum layer 461.
  • the calcium silicide layer 421 and the aluminum layer 461 become sources that generate calcium vapor and aluminum vapor, respectively.
  • an alumina support 425 was disposed at the bottom of the alumina container 410 so as not to interfere with the first and second alumina containers 420 and 460.
  • the support body 425 has a flat portion provided at the top.
  • an alumina plate 428 having a thickness of 1 mm was disposed on the flat portion of the support 425.
  • the alumina container 410 has a substantially cylindrical shape with an outer diameter of 40 mm, an inner diameter of 38 mm, and a height of 40 mm.
  • the first carbon container 430 has a substantially cylindrical shape with an outer diameter of 60 mm, an inner diameter of 50 mm, and a height of 60 mm, and the second carbon container 450 has an outer diameter of 80 mm ⁇ an inner diameter of 70 mm ⁇ a height of 75 mm. It has a cylindrical shape.
  • black material D13 a black material having a black surface
  • the black material D13 could be easily recovered.
  • the relative density of the black material D13 was 95.5%.
  • the black material D13 is a conductive mayenite compound having a high electron density.
  • Example 51 An attempt was made to produce a high electron density conductive mayenite compound by the same method as in Example 1 above.
  • Example 51 the heat treatment of the object to be processed was performed in an environment where the calcium silicide layer 320 does not exist. Further, when the object to be processed was heat-treated, the inside of the furnace was evacuated and reduced in pressure to 100 Pa, and then nitrogen gas having an oxygen concentration of 1 volume ppm or less was allowed to flow into the furnace until atmospheric pressure was reached. Other conditions are the same as in Example 1.
  • a black material having a dark surface (hereinafter referred to as a black material “D51”) was obtained after the above-described step (manufacturing the conductive mayenite compound).
  • the black material D51 is not a conductive mayenite compound having a high electron density.
  • Example 52 An attempt was made to produce a high electron density conductive mayenite compound by the same method as in Example 1 above.
  • Example 52 the object to be treated was heat-treated without using the alumina block 325 and the alumina plate 328 in the apparatus 300 in the above-described process (manufacturing the conductive mayenite compound). That is, in Example 52, the compact C1 of the mayenite compound was directly placed on the calcium silicide layer 320 and subjected to heat treatment.
  • a black material having a dark surface (hereinafter referred to as a black material “D52”) was obtained after the above-described step (manufacturing the conductive mayenite compound).
  • the black material D52 is in a state of sinking in the calcium silicide layer 320, and a great deal of labor is required for recovery. Therefore, it was found that this method is not suitable for industrial production.
  • Table 1 below collectively shows the specifications, heat treatment conditions, evaluation results, and the like of the objects to be processed in Examples 1 to 13 and Examples 51 to 52.
  • the numerical value in the “F addition amount (x value)” column represents the amount of fluorine (F) contained in the object to be processed. This value is finally calculated from the object to be processed by the following formula (4) (12-x) CaO ⁇ 7Al 2 O 3 ⁇ xCaF 2 (4) equation The value of x when assuming that the mayenite compound represented by this was manufactured is meant.
  • the present invention can be applied to a method for producing a conductive mayenite compound that can be used for a sputtering target, a fluorescent lamp, or the like necessary for forming a thin film of an electron injection layer of an organic EL element.

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Abstract

L'invention concerne un procédé de fabrication d'un composé de mayénite conducteur de façon électrique, le procédé étant caractérisé en ce qu'il a : une étape (a) pour préparer un article à traiter, l'article à traiter contenant un composé de mayénite ou un précurseur d'un composé de mayénite ; et une étape (b) pour traiter thermiquement l'article à traiter dans un environnement d'une atmosphère réductrice, une matière composite et/ou un alliage étant présent dans l'environnement, l'article à traiter étant disposé dans un état sans contact avec la matière composite et/ou l'alliage, et la matière composite et/ou l'alliage contenant au moins un élément choisi dans le groupe consistant en calcium (Ca), magnésium (Mg), lithium (Li), aluminium (Al), silicium (Si), titane (Ti), vanadium (V), manganèse (Mn), chrome (Cr), sodium (Na) et gallium (Ga).
PCT/JP2013/080446 2012-11-14 2013-11-11 Procédé de fabrication de composé de mayénite conducteur de façon électrique Ceased WO2014077215A1 (fr)

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WO2018021282A1 (fr) * 2016-07-25 2018-02-01 国立大学法人東京工業大学 Procédé de fabrication d'un composé de mayénite en forme d'électrure
CN108855121A (zh) * 2018-05-16 2018-11-23 芜湖市创源新材料有限公司 一种镍基催化空气净化剂的制备方法

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JP7161648B2 (ja) * 2019-02-08 2022-10-27 栃木県石灰工業協同組合 ドロマイトを原料としたマイエナイトーマグネシアコンポジットの創製

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WO2006129675A1 (fr) * 2005-05-30 2006-12-07 Asahi Glass Company, Limited Processus de production de compose mayenite conducteur
JP2012025636A (ja) * 2010-07-26 2012-02-09 Tokyo Institute Of Technology 二酸化炭素の吸着還元剤及び還元方法
WO2012077658A1 (fr) * 2010-12-07 2012-06-14 国立大学法人東京工業大学 Catalyseur de synthèse d'ammoniac et procédé de synthèse d'ammoniac

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WO2006129675A1 (fr) * 2005-05-30 2006-12-07 Asahi Glass Company, Limited Processus de production de compose mayenite conducteur
JP2012025636A (ja) * 2010-07-26 2012-02-09 Tokyo Institute Of Technology 二酸化炭素の吸着還元剤及び還元方法
WO2012077658A1 (fr) * 2010-12-07 2012-06-14 国立大学法人東京工業大学 Catalyseur de synthèse d'ammoniac et procédé de synthèse d'ammoniac

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WO2018021282A1 (fr) * 2016-07-25 2018-02-01 国立大学法人東京工業大学 Procédé de fabrication d'un composé de mayénite en forme d'électrure
CN109476494A (zh) * 2016-07-25 2019-03-15 国立大学法人东京工业大学 电子晶体化钙铝石型化合物的制备方法
KR20190032416A (ko) * 2016-07-25 2019-03-27 고쿠리츠다이가쿠호진 토쿄고교 다이가꾸 전자화물화 마이에나이트형 화합물의 제조 방법
JPWO2018021282A1 (ja) * 2016-07-25 2019-06-13 国立大学法人東京工業大学 エレクトライド化マイエナイト型化合物の製造方法
CN109476494B (zh) * 2016-07-25 2021-01-26 国立研究开发法人科学技术振兴机构 电子晶体化钙铝石型化合物的制备方法
KR102309473B1 (ko) 2016-07-25 2021-10-05 고쿠리츠켄큐카이하츠호진 카가쿠기쥬츠신코키코 전자화물화 마이에나이트형 화합물의 제조 방법
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CN108855121A (zh) * 2018-05-16 2018-11-23 芜湖市创源新材料有限公司 一种镍基催化空气净化剂的制备方法

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