JP6125810B2 - ナノ粒子を含む三成分熱電材料及びその製造方法 - Google Patents
ナノ粒子を含む三成分熱電材料及びその製造方法 Download PDFInfo
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- 239000000463 material Substances 0.000 title claims description 150
- 239000002105 nanoparticle Substances 0.000 title claims description 110
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 127
- 239000002184 metal Substances 0.000 claims description 124
- 239000004065 semiconductor Substances 0.000 claims description 80
- 239000011159 matrix material Substances 0.000 claims description 68
- 239000000203 mixture Substances 0.000 claims description 65
- 229910052714 tellurium Inorganic materials 0.000 claims description 34
- 150000002739 metals Chemical class 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 27
- 239000002245 particle Substances 0.000 claims description 27
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 27
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 26
- 239000002244 precipitate Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 23
- 239000003638 chemical reducing agent Substances 0.000 claims description 22
- 239000011669 selenium Substances 0.000 claims description 22
- 229910052711 selenium Inorganic materials 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 150000002736 metal compounds Chemical class 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- 239000012736 aqueous medium Substances 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 230000007423 decrease Effects 0.000 claims description 7
- -1 selenium metals Chemical class 0.000 claims description 7
- 238000005245 sintering Methods 0.000 claims description 7
- 239000012279 sodium borohydride Substances 0.000 claims description 7
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 7
- 150000004703 alkoxides Chemical class 0.000 claims description 5
- 229910001849 group 12 element Inorganic materials 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 150000004820 halides Chemical class 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 3
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims 1
- 239000002243 precursor Substances 0.000 description 37
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 32
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000006185 dispersion Substances 0.000 description 17
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 description 17
- 238000006722 reduction reaction Methods 0.000 description 16
- 239000011787 zinc oxide Substances 0.000 description 16
- 230000009467 reduction Effects 0.000 description 15
- 230000003647 oxidation Effects 0.000 description 14
- 238000007254 oxidation reaction Methods 0.000 description 14
- 150000003346 selenoethers Chemical class 0.000 description 12
- 239000000919 ceramic Substances 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000011261 inert gas Substances 0.000 description 9
- 229910052797 bismuth Inorganic materials 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000002131 composite material Substances 0.000 description 7
- 239000002612 dispersion medium Substances 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 5
- 150000004770 chalcogenides Chemical class 0.000 description 5
- 239000002019 doping agent Substances 0.000 description 5
- 238000013507 mapping Methods 0.000 description 5
- RBRLCUAPGJEAOP-UHFFFAOYSA-M sodium selanide Chemical compound [Na+].[SeH-] RBRLCUAPGJEAOP-UHFFFAOYSA-M 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 150000004696 coordination complex Chemical class 0.000 description 4
- 239000011258 core-shell material Substances 0.000 description 4
- 230000000875 corresponding effect Effects 0.000 description 4
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 238000001465 metallisation Methods 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 239000002070 nanowire Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- KKMOSYLWYLMHAL-UHFFFAOYSA-N 2-bromo-6-nitroaniline Chemical compound NC1=C(Br)C=CC=C1[N+]([O-])=O KKMOSYLWYLMHAL-UHFFFAOYSA-N 0.000 description 3
- 229910001152 Bi alloy Inorganic materials 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 150000004772 tellurides Chemical class 0.000 description 3
- 230000005676 thermoelectric effect Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- 239000012448 Lithium borohydride Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000009969 flowable effect Effects 0.000 description 2
- 238000009499 grossing Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012280 lithium aluminium hydride Substances 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000615 nonconductor Substances 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- QEBDLIWRLCPLCY-UHFFFAOYSA-N selanylidenebismuth Chemical compound [Bi]=[Se] QEBDLIWRLCPLCY-UHFFFAOYSA-N 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- 230000005678 Seebeck effect Effects 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- 229910001215 Te alloy Inorganic materials 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001462 antimony Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002106 nanomesh Substances 0.000 description 1
- 239000007783 nanoporous material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- IIQJBVZYLIIMND-UHFFFAOYSA-J potassium;antimony(3+);2,3-dihydroxybutanedioate Chemical compound [K+].[Sb+3].[O-]C(=O)C(O)C(O)C([O-])=O.[O-]C(=O)C(O)C(O)C([O-])=O IIQJBVZYLIIMND-UHFFFAOYSA-J 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000010405 reoxidation reaction Methods 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- ZIJTYIRGFVHPHZ-UHFFFAOYSA-N selenium oxide(seo) Chemical class [Se]=O ZIJTYIRGFVHPHZ-UHFFFAOYSA-N 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- MQRWPMGRGIILKQ-UHFFFAOYSA-N sodium telluride Chemical compound [Na][Te][Na] MQRWPMGRGIILKQ-UHFFFAOYSA-N 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/007—Tellurides or selenides of metals
-
- 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
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/547—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on sulfides or selenides or tellurides
-
- 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
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
- C04B35/645—Pressure sintering
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/10—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects
- H10N10/17—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects characterised by the structure or configuration of the cell or thermocouple forming the device
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/851—Thermoelectric active materials comprising inorganic compositions
- H10N10/852—Thermoelectric active materials comprising inorganic compositions comprising tellurium, selenium or sulfur
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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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
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3284—Zinc oxides, zincates, cadmium oxides, cadmiates, mercury oxides, mercurates or oxide forming salts thereof
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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
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3298—Bismuth oxides, bismuthates or oxide forming salts thereof, e.g. zinc bismuthate
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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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
- C04B2235/449—Organic acids, e.g. EDTA, citrate, acetate, oxalate
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Powder Metallurgy (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Description
ZT=S2γT/κ
上記式中のZTもしくは性能指数は、ゼーベック係数S、電気伝導率γ及び熱伝導率κを含む材料の巨視的輸送パラメータに関連している。
本発明は、三成分主族マトリックス材料及びナノ粒子及び/又はナノ内在物を含む熱電材料を包含する。ナノ粒子の例は、式MO及び/又はM(式中、Mは2+酸化状態又は金属形態の2族もしくは12族元素である)を有する材料の粒子を含む。マトリックス材料は三成分主族又はカルコゲニド半導体材料であり、好ましくは元素Bi、Se及びTeを含み、好ましくは式Bi 2 (SeTe) 3 を有する材料である。半導体マトリックス材料はテルル化ビスマスとセレンのような他の元素(例えば高い導電性を与える元素)との合金、又は適切な熱電効果を有する他の材料であってよい。この熱電材料は、変換効率の高い熱電デバイスに用いることのできる、高い性能指数を有する材料を含む。
酸素を含まないフラスコに5.611gの200メッシュテルル粉末、0.184gの100メッシュセレン粉末及び103mLの水を加えた。この混合物を不活性ガスで脱気し、氷水槽中で冷却した。6.360gのホウ化水素ナトリウムを少しずつ加えた。危険な熱の発生及び水素ガスの発火を防ぐために、ホウ化水素ナトリウムは一度に加えなかった。
[1]
三成分主族半導体材料、及び
式MO(式中、Mは2族元素及び12族元素からなる群より選ばれる少なくとも1種の元素である)の金属酸化物のナノ粒子
を含み、前記ナノ粒子が三成分主族半導体材料のマトリックス中に分散している熱電組成物。
[2]
前記半導体材料がBi、Te及びSeを含む、項目1記載の熱電組成物。
[3]
前記半導体材料がBi 2 (SeTe) 3 を含む、項目1記載の熱電組成物。
[4]
前記半導体材料が、この半導体材料の総重量を基準として少なくとも50wt%の量のBi 2 (SeTe) 3 を含む、項目1記載の熱電組成物。
[5]
前記半導体材料がBi 2 (SeTe) 3 を含み、前記ナノ粒子がZnOナノ粒子を含む、項目1記載の熱電組成物。
[6]
前記半導体材料が、この半導体材料の総重量を基準として少なくとも50wt%の量のBi 2 (SeTe) 3 を含み、前記ナノ粒子の総重量を基準として少なくとも50wt%がZnOの粒子である、項目1記載の熱電組成物。
[7]
還元された化合物の形態の少なくとも1種の金属を酸化された化合物の形態の少なくとも1種の金属と混合することを含む、N型熱電材料の製造方法であって、前記混合が主族金属の少なくとも3種の異なる金属化合物を混合することを含み、前記混合が水中において式MO(式中、Mは周期表の2族元素又は12族元素である)の材料のナノ粒子の存在下において行う方法。
[8]
金属粉末の形態の金属を1種以上の還元剤と水中で反応させることにより、混合前に少なくとも2種の還元された金属化合物を形成することをさらに含む、項目7記載の方法。
[9]
水溶液及び有機溶液からなる群より選ばれる少なくとも1種と混合することにより形成される沈殿を洗浄することをさらに含む、項目7記載の方法。
[10]
洗浄した沈殿を乾燥させ、次いで
この洗浄した沈殿をプレス成形し、そして
圧縮した洗浄した沈殿を焼結して、ナノ粒子を含む焼結した三成分N型熱電材料を形成すること、
をさらに含む、項目9記載の方法。
[11]
前記還元された金属化合物が、アルカリ性水性媒体中においてテルル金属とセレンの混合物をホウ化水素ナトリウムと反応させることにより形成される、項目7記載の方法。
[12]
酸化された金属化合物を含む水性組成物を2種の還元された金属の混合物と混合することを含む、項目7記載の方法。
[13]
酸化された金属化合物がハロゲン化物、アルコキシド、カルボキシレート又はこれらの混合物の少なくとも1種の形態である、項目12記載の方法。
Claims (16)
- 式(BiSe) 2 Te 3 の三成分主族半導体材料、及び
ZnOナノ粒子
を含み、前記ナノ粒子が三成分主族半導体材料のマトリックス中に分散している熱電組成物であって、150℃から200℃の温度範囲にかけて電気伝導率が低下し、150℃から200℃の温度範囲にかけてゼーベック係数が一定となる熱電組成物。 - 前記ZnOナノ粒子が単峰型粒度分布を有する、請求項1記載の熱電組成物。
- 前記ZnOナノ粒子が三成分主族半導体材料の総重量に対して40重量%以下の量で熱電組成物中に存在する、請求項1記載の熱電組成物。
- 前記ZnOナノ粒子が三成分主族半導体材料の総重量に対して60重量%以上の量で熱電組成物中に存在する、請求項1記載の熱電組成物。
- 前記ZnOナノ粒子が0.95〜0.99の球形度を有する、請求項1記載の熱電組成物。
- N型熱電材料の製造方法であって、
金属粉末の形態の金属を1種以上の還元剤と水中で反応させることにより、混合前に少なくとも2種の還元された金属化合物を形成すること、次いで
還元された金属化合物を酸化された化合物の形態の少なくとも1種の金属と混合することを含み、前記混合が主族金属の少なくとも3種の異なる金属化合物を混合することを含み、前記混合が水中において式MO(式中、Mは周期表の2族元素又は12族元素である)の材料のナノ粒子の存在下において行う方法。 - 水溶液及び有機溶液からなる群より選ばれる少なくとも1種と混合することにより形成される沈殿を洗浄することをさらに含む、請求項6記載の方法。
- 洗浄した沈殿を乾燥させ、次いで
この洗浄した沈殿をプレス成形し、そして
圧縮した洗浄した沈殿を焼結して、ナノ粒子を含む焼結した三成分N型熱電材料を形成すること、
をさらに含む、請求項7記載の方法。 - 前記還元された金属化合物が、アルカリ性水性媒体中においてテルル金属とセレン金属の混合物をホウ化水素ナトリウムと反応させることにより形成される、請求項6記載の方法。
- 酸化された金属化合物がハロゲン化物、アルコキシド、カルボキシレート又はこれらの混合物の少なくとも1種の形態である、請求項6記載の方法。
- 第1の電気伝導性層と接触している熱源、第1の電気伝導性層と接触している第1及び第2の熱電材料、第1及び第2の熱電材料と接触している第1及び第2の電気接触、及び熱シンクを含む熱電デバイスであって、前記第1の熱電材料が請求項1記載の熱電組成物を含む熱電デバイス。
- 請求項1記載の熱電組成物の製造方法であって、
還元された形態のTe及びSe金属化合物を混合して混合物を形成すること、及び
この混合物を400℃及び100MPaにおいて4時間焼結することを含み、前記混合をZnOナノ粒子の存在下において行う方法。 - 混合する前に、金属粉末の形態のTe及びSe金属を1種以上の還元剤及び水と反応させることにより還元されたTe及びSe金属化合物を形成することをさらに含む、請求項12記載の方法。
- 水溶液及び有機溶液からなる群より選ばれる少なくとも1種と混合することにより形成される沈殿を洗浄することをさらに含む、請求項12記載の方法。
- 洗浄した沈殿を乾燥させ、次いで
この洗浄した沈殿をプレス成形し、そして
圧縮した洗浄した沈殿を焼結して、ZnOナノ粒子を含む焼結した三成分N型熱電材料を形成すること、
をさらに含む、請求項14記載の方法。 - 前記還元された金属化合物が、アルカリ性水性媒体中においてテルル金属とセレン金属の混合物をホウ化水素ナトリウムと反応させることにより形成される、請求項12記載の方法。
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