WO2018124660A1 - 신규한 화합물 반도체 및 그 활용 - Google Patents
신규한 화합물 반도체 및 그 활용 Download PDFInfo
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- WO2018124660A1 WO2018124660A1 PCT/KR2017/015374 KR2017015374W WO2018124660A1 WO 2018124660 A1 WO2018124660 A1 WO 2018124660A1 KR 2017015374 W KR2017015374 W KR 2017015374W WO 2018124660 A1 WO2018124660 A1 WO 2018124660A1
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 114
- 239000004065 semiconductor Substances 0.000 title claims abstract description 85
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 18
- 229910020712 Co—Sb Inorganic materials 0.000 claims abstract description 17
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 17
- 229910052718 tin Inorganic materials 0.000 claims abstract description 16
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 12
- 239000011148 porous material Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 24
- 238000005245 sintering Methods 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 229910052787 antimony Inorganic materials 0.000 claims description 5
- 239000011800 void material Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 29
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 13
- 239000011669 selenium Substances 0.000 description 12
- 239000002994 raw material Substances 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000002800 charge carrier Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 238000002490 spark plasma sintering Methods 0.000 description 3
- 229940074389 tellurium Drugs 0.000 description 3
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 3
- 241000218033 Hibiscus Species 0.000 description 2
- 235000005206 Hibiscus Nutrition 0.000 description 2
- 235000007185 Hibiscus lunariifolius Nutrition 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910004613 CdTe Inorganic materials 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- 230000005679 Peltier effect Effects 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
- FAWGZAFXDJGWBB-UHFFFAOYSA-N antimony(3+) Chemical compound [Sb+3] FAWGZAFXDJGWBB-UHFFFAOYSA-N 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000037213 diet Effects 0.000 description 1
- 235000005911 diet Nutrition 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000000313 electron-beam-induced deposition Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 235000015047 pilsener Nutrition 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/0272—Selenium or tellurium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- 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
- H10N10/01—Manufacture or treatment
-
- 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
-
- 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
- H10N10/853—Thermoelectric active materials comprising inorganic compositions comprising arsenic, antimony or bismuth
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N99/00—Subject matter not provided for in other groups of this subclass
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- thermoelectric conversion element may be applied to thermoelectric conversion power generation or thermoelectric conversion cooling, among which thermoelectric conversion power generation converts thermal energy into electrical energy by using thermoelectric power generated by placing a temperature difference in the thermoelectric conversion element. It is a form of development.
- thermoelectric conversion element The energy conversion efficiency of such a thermoelectric conversion element depends on ZT, which is a figure of merit value of the thermoelectric conversion material.
- ZT is determined according to Seebeck coefficient, electrical conductivity, thermal conductivity, etc. More specifically, ZT is proportional to the square and electrical conductivity of the Seebeck coefficient and inversely proportional to the thermal conductivity. Therefore, in order to increase the energy conversion efficiency of the thermoelectric conversion element, it is necessary to develop a thermoelectric conversion material having high Seebeck coefficient or high electrical conductivity or low thermal conductivity.
- compound semiconductor solar cells use compound semiconductors in the light absorption layer that absorbs sunlight to generate electron-hole pairs, and in particular, group V compound semiconductors such as GaAs, InP, GaAlAs, GalnAs, CdS, CdTe, ZnS, etc.
- group V compound semiconductors such as GaAs, InP, GaAlAs, GalnAs, CdS, CdTe, ZnS, etc.
- Group VI compound semiconductors, Group m compound semiconductors represented by CuInSe2, and the like can be used.
- the light absorbing layer of the solar cell is required to be excellent in long-term electrical and optical stability, high photoelectric conversion efficiency, and to easily adjust band gap energy or conductivity by changing composition or doping.
- requirements such as manufacturing cost and yield must also be satisfied.
- many conventional compound semiconductors do not meet all of these requirements together.
- thermoelectric conversion material such as thermoelectric conversion material, solar cell, etc. of the thermoelectric conversion element
- thermoelectric conversion element such as thermoelectric conversion material, solar cell, etc.
- An object of the present invention is to provide a conventional thermoelectric conversion element, a solar cell, and the like.
- the present inventors after repeated studies on the compound semiconductor, the C Sb Scutherdite compound; Sn and S contained in the internal void of the Co-Sb skater diet compound; And a C substituted with Sb of the Sb Scutterudite compound, and having successfully synthesized a compound semiconductor represented by Formula 1, wherein the compound is a thermoelectric conversion material of a thermoelectric conversion element or a solar cell. Confirmed that the light absorbing layer can be used to complete the present invention.
- the compound semiconductor represented by Formula 1 wherein the compound is a thermoelectric conversion material of a thermoelectric conversion element or a solar cell.
- the present invention provides a Co-Sb scrutherite compound; Sn and S contained in the internal pores of the C Sb Scutherdite compound; And a Q substituted with Sb of the Co-Sb scrutherite compound, and represented by Chemical Formula 1 as follows.
- Q is one or more selected from the group consisting of 0, Se, and Te, and 0 ⁇ x ⁇ 0.2, 0 ⁇ y ⁇ l, and 0 ⁇ z ⁇ 12. At least one element selected from the group consisting of 0, Se, and Te may mean 0, Se, Te alone, or a mixture of two or more thereof.
- Sn is an element symbol representing a tin (t in) element
- S is an element symbol representing a sulfur element
- Co is an element symbol representing a cobalt element
- Sb is an element symbol representing an ant imony element
- Q is substituted for at least one element selected from the group consisting of oxygen, selenium, and tellurium
- X is a relative molar ratio of the tin element
- y is a relative molar ratio of the sulfur element
- z is oxygen, selenium, and tellurium (tel lur ium).
- Q may be Se or Te.
- Q in Formula 1 may be Te.
- X may be 0.01 ⁇ x ⁇ 0.18.
- X is preferably 0.05 ⁇ x ⁇ 0.15.
- thermoelectric performance may decrease.
- y is 0 ⁇ y ⁇ 0.5.
- the present inventors have conducted research on an N-type scudrudite thermoelectric material having excellent thermoelectric performance, multi-layered the elements of Sn and S as a layering material on a Co-Sb scudrudite compound, and specified the Sb site. In the case of doping the charge compensation material, the experiments confirmed that the lattice thermal conductivity was lowered and the output factor increased to show high thermoelectric conversion efficiency.
- the scrutherite compound may have a unit lattice structure as shown in FIG. 2, specifically, in the unit lattice, metal atoms are located at eight vertices, and four nonmetallic atoms have a planar structure therein. It may contain six cube structures, two metal atoms located at eight vertices, and two empty cube structures.
- Sn and S elements are filled in the voids included in the unit grid of Co-Sb scrutherite compound with a filler as shown in FIG. 1 to induce a rattling effect.
- This can reduce the lattice thermal conductivity, control the charge carrier concentration to an optimal level through the chemical properties of supplying additional electrons through Sn and holes through S.
- the lattice thermal conductivity is reduced, and the N-type scutterudite thermoelectric material with improved output factor is more effective. It can exhibit improved thermoelectric properties.
- the doping amount z of has a value in the range of 0 ⁇ z ⁇ 12. In particular, when the doping amount z value exceeds 0.2, since the thermoelectric properties may be reduced by the formation of the secondary phase, 0 ⁇ z ⁇ 0.2 is preferable.
- the N-type scudrudite thermoelectric material in which a specific charge compensation material is substituted (doped) at Sb can be optimized by controlling the charge carrier concentration, and has a higher thermoelectric performance index ZT by reducing the lattice thermal conductivity. Can be.
- the charge is substituted (doped) at the Sb site.
- Te or Se as a compensating material, which is different in detail depending on the degree of ionization of each atom in the N-type contemplatruded thermoelectric material, and in the case of Te or Se, the concentration of electrons provided therefrom This is because of its high level, which can provide additional electrons and control and optimize the charge carrier concentration.
- thermoelectric material substituted (doped) at the Sb site when Sn is used as the charge compensation material substituted (doped) at the Sb site, the concentration of electrons provided from Sn is small to provide additional holes, which is suitable for P-type scrutherite thermoelectric materials, and There are limitations in that it is difficult to use as a type scutterrudite thermoelectric material.
- the compound semiconductor of the embodiment may include a Co— Sb skaterite compound; Sn and S contained in the internal void of the said Co-Sb scerrudite compound; And it may include a Q substituted with Sb of the Co-Sb casterudite compound.
- the compound semiconductor of the embodiment may be used as an N-type compound semiconductor.
- the compound semiconductor of Formula 1 includes Sn and S together ; The high stability to oxidation even at high temperatures, while minimizing the process cost, not only can improve the durability in the thermoelectric models, but also can significantly improve the thermal conductivity of the compound semiconductor of Formula 1 to implement improved thermoelectric performance.
- the molar ratio of X to 1 mole of y in Formula 1 is 0. 1 mol to 0.9 mol, or 0.2 mol to 0.8 mol, or 0.25 mol to 0.75 mol. Remind When the molar ratio of X to mole of y in Formula 1 is greater than 0.9, as the thermal conductivity of the compound semiconductor of Chemical Formula 1 increases rapidly, thermoelectric performance may decrease. In addition, when the molar ratio of X to 1 mol of y in the general formula (1) decreases to less than 0.1, the content of Sn in the compound semiconductor of the general formula (1) is not sufficient, and the effect of adding Sn is sufficiently It is difficult.
- z is 0 ⁇ z ⁇ 4.
- z may be 0 ⁇ 2 ⁇ 5. Most preferably, ⁇ in Chemical Formula 1 is 0 ⁇ 1.5.
- the compound semiconductor represented by Formula 1 may include a part of the secondary phase, the amount may vary depending on the heat treatment conditions.
- the compound semiconductor according to the present invention comprises the steps of forming a mixture comprising at least one element selected from the group consisting of 0, Se, and Te, Sn, S, Co, and Sb, and heat-treating the mixture. It can be prepared to include. At least one element selected from the group consisting of 0, Se, and Te may mean 0, Se, Te alone, or a combination of two or more thereof.
- each raw material to be mixed in the mixture forming step may be in the form of a powder, the present invention is not necessarily limited by the specific form of such a mixed raw material.
- the heat treatment step may be performed in a vacuum or by arranging a gas such as Ar, He, N 2 , which contains some hydrogen or does not contain hydrogen.
- the heat treatment temperature may be 400 ° C to 800 ⁇ .
- the heat treatment temperature may be 450 ° C to 700 ° C. More preferably, the heat treatment temperature may be 500 ° C to 700 ° C.
- the heat treatment step may include two or more heat treatment steps.
- the second heat treatment may be performed at a second temperature of the complex formed in the step of forming the mixture, that is, mixing raw materials. have.
- the heat treatment step may include three heat treatment steps of a first heat treatment step, a second heat treatment step, and a third heat treatment step.
- the first heat treatment step may be performed at a temperature range of 400 ° C to 600 ° C
- the second heat treatment step and the third heat treatment step may be performed at a temperature range of 600 ° C to 800 ° C.
- the first heat treatment step may be performed during the formation of the mixture in which the raw materials are mixed
- the second heat treatment step and the third heat treatment step may be sequentially performed thereafter.
- the heat treatment step may include the step of subjecting the heat treated mixture.
- the engraving step is carried out to reach the temperature of the heat-treated mixture to room temperature (about 20 ° C to 30 ° C), it is possible to use a variety of conventional cooling methods or relief devices known in the art.
- the heat treatment, or if necessary, after the heat treatment, the mixture may be further subjected to further pressure sintering step.
- An example of a specific method of performing the pressure sintering step is not particularly limited, but preferably, a hot press method or a spark plasma sintering (SPS) method may be used.
- the pressure sintering step may be performed for 10 minutes to 60 minutes at a silver degree of 500 ° C. to 700 and a pressure of 20 MPa to 50 MPa.
- the sintering temperature is less than 500 ° C. or the sintering time and pressure is low, a high density sintered body cannot be obtained. High pressures are also undesirable because they can pose a risk for the application mold and equipment.
- Spark Plasma Sintering is a method of sintering a powder or sheet by applying a DC pils current in a direction parallel to the pressing direction while pressing the powder or sheet in one axis. This is a sintering method that applies high energy of plasma generated by the spark generated at this time and electric field diffusion, thermal diffusion, etc.
- the discharge plasma sintering method has a lower sintering temperature and can be completed in a short time including the temperature and the holding time, compared to the conventional hot press method, so that the power consumption is greatly reduced and the handling is easy. , Running Course It is cheap.
- the pressure sintering step may further comprise the step of pulverizing the cooled mixture after heat treatment or heat treatment as necessary.
- the grinding method are not particularly limited, and various grinding methods or grinding devices known in the art may be applied without limitation.
- thermoelectric conversion element according to the present invention may include the compound semiconductor described above. That is, the compound semiconductor according to the present invention can be used as a thermoelectric conversion material of the thermoelectric conversion element.
- the compound semiconductor according to the present invention has a large ⁇ , which is a performance index value of the thermoelectric conversion material.
- the Seebeck coefficient and electrical conductivity are large, and the thermal conductivity is low, so the thermoelectric conversion performance is excellent. Therefore, the compound semiconductor according to the present invention can be usefully used in thermoelectric conversion elements in place of conventional thermoelectric conversion materials or in addition to conventional compound semiconductors.
- the solar cell according to the present invention may include the compound semiconductor described above. That is, the compound semiconductor according to the present invention can be used as a light absorbing layer of a solar cell, especially a solar cell.
- the solar cell can be manufactured in a structure in which a front transparent electrode, a buffer layer, a light absorbing layer, a back electrode, a substrate, and the like are sequentially stacked from the side where sunlight is incident.
- the engine located at the bottom may be made of glass, and the back electrode formed entirely thereon may be formed by depositing a metal such as Mo.
- the light absorbing layer may be formed by stacking the compound semiconductor according to the present invention on the back electrode by an electron beam deposition method, a sol-gel method, or a PLLKpulse laser deposition method.
- a buffer layer which completes the lattice constant difference and the band gap difference between the ZnO layer and the light absorbing layer, which are used as the front transparent electrode. It may be formed by depositing by a method such as ion).
- a front transparent electrode may be formed on the buffer layer by sputtering or the like as a laminated film of ZnO or ZnO and ITC).
- the solar cell according to the present invention may be variously modified.
- Example it is possible to manufacture a laminated solar cell in which a solar cell using the compound semiconductor according to the present invention as a light absorbing layer is laminated.
- the other solar cells stacked in this way may use solar cells using silicon or other known compound semiconductors.
- the band gap of the compound semiconductor of the present invention a plurality of solar cells using compound semiconductors having different band gaps as the light absorbing layer can be laminated.
- the band gap of the compound semiconductor according to the present invention can be controlled by changing the composition ratio of the constituent elements, in particular Te, which constitute the compound.
- the compound semiconductor according to the present invention may be applied to an infrared window (IR window) or an infrared sensor that selectively passes infrared rays.
- IR window infrared window
- infrared sensor that selectively passes infrared rays.
- a novel compound semiconductor material is provided. According to one aspect of the present invention, such a novel compound semiconductor can be used as another material to replace the conventional compound semiconductor or in addition to the conventional compound semiconductor.
- thermoelectric conversion performance of the compound semiconductor is good, and thus may be usefully used in the thermoelectric conversion device.
- the compound semiconductor according to the present invention can be used as a thermoelectric conversion material of the thermoelectric conversion element.
- a compound semiconductor can be used in a solar cell.
- the compound semiconductor according to the present invention can be used as a light absorption layer of a solar cell.
- the compound semiconductor may be used in an infrared window (IR window) for selectively passing infrared rays, an infrared sensor, a magnetic element, a memory, and the like.
- IR window infrared window
- the compound semiconductor may be used in an infrared window (IR window) for selectively passing infrared rays, an infrared sensor, a magnetic element, a memory, and the like.
- Figure 1 shows a unit grid of the compound of Example 1.
- Figure 2 shows the unit grid of the skudrudite compound.
- Co 4 Sb 12 scerrudite compound The Co 4 Sb 12 hibiscus Teruel die agent compound is Sn, and S are layered inside the pores of the Co 4 Sb 12 hibiscus Teruel die bit Sb compound of Sno.osS ⁇ Co A Sbn.Jeo.s Te doped in the It synthesize
- the synthesized compound was filled in a graphite mold for discharging plasma and then discharged and plasma sintered for 10 minutes at a temperature of 650 " C and 50 MPa to manufacture the compound semiconductor of Example 1.
- the compound peninsula The relative density of the sieves was determined to be at least 98%.
- a compound semiconductor was manufactured in the same manner as in Example 1, except that the complex composition was changed to Sno.iSo.sCo ⁇ bn. ⁇ Eo.ij.
- Example 3
- composition of the composition was Sno. ⁇ o . i ⁇ Sbu. ⁇ eo .
- a compound semiconductor was manufactured in the same manner as in Example 1, except that s was changed to s. Comparative Examples 1 to 3: Preparation of Compound Semiconductor Comparative Example 1
- a compound semiconductor was manufactured according to the same method as Example 1 except for changing to So.z MSbu Teo.e. Comparative Example 2
- Example 2 A compound semiconductor was manufactured in the same manner as in Example 1, except that the mixture composition was changed to Sno.sSo.zCo ⁇ bn.Jeo.e. ⁇ Experimental Example: Measurement of Physical Properties of Compound Semiconductors Obtained in Examples and Comparative Examples> The physical properties of the compound semiconductors obtained in Examples and Comparative Examples were measured by the following methods, and the results are shown in Tables 1 and 2.
- the compound semiconductors obtained in Examples and Comparative Examples were processed into coin-types having a diameter of 12.7 mm and a height of 1.5 mm 3 to prepare specimens. Then, for the specimen, the thermal conductivity was calculated from the measured values of thermal diffusivity, specific heat and density by the laser flash method (Netzsch, LFA-457) in the range of 50 ° C to 500 ° C. The lattice thermal conductivity was also obtained by calculating and applying the calculated value to the calculated thermal conductivity, and the results are shown in Table 1 below.
- the compound semiconductors obtained in Examples and Comparative Examples were processed into rectangul ar-types having a width of 3 mm, a length of 3 mm, and a height of 12 mm 3 to prepare a specimen. Then, the electrical conductivity and the Seebeck coefficient of the specimens were measured using ZEM-3 J1 vac- Ri co, Inc) in the range of 50 ° C to 500 ° C.
- ZT thermoelectric performance index
- ⁇ the electrical conductivity
- S the Seebeck coefficient
- ⁇ the temperature
- ⁇ the thermal conductivity
- the compound semiconductors of Examples 1 to 3 were confirmed to improve the thermoelectric performance index as compared to Comparative Examples 1 and 2 over the entire temperature measurement interval as Sn and S layered at the same time.
- thermoelectric performance index is significantly lower than that of the embodiment, making it difficult to apply as a thermoelectric material.
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EP17886732.1A EP3447812B1 (en) | 2016-12-28 | 2017-12-22 | Novel compound semiconductor and use thereof |
CN201780025805.3A CN109275341B (zh) | 2016-12-28 | 2017-12-22 | 化合物半导体及其用途 |
JP2018552661A JP6775841B2 (ja) | 2016-12-28 | 2017-12-22 | 新規な化合物半導体およびその活用 |
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