TW202016326A - 熱電合金及其製作方法與熱電合金複合物 - Google Patents
熱電合金及其製作方法與熱電合金複合物 Download PDFInfo
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- 239000000956 alloy Substances 0.000 title claims abstract description 141
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- 230000008569 process Effects 0.000 claims abstract description 55
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052714 tellurium Inorganic materials 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 229910052738 indium Inorganic materials 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 229910052733 gallium Inorganic materials 0.000 claims description 7
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- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 7
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- 229910052732 germanium Inorganic materials 0.000 claims description 6
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- 230000001590 oxidative effect Effects 0.000 claims description 6
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 4
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 238000007747 plating Methods 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
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- 238000007789 sealing Methods 0.000 abstract description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 20
- 238000012360 testing method Methods 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 10
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- 239000002184 metal Substances 0.000 description 8
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- 229910052785 arsenic Inorganic materials 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 230000002708 enhancing effect Effects 0.000 description 4
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- 239000012535 impurity Substances 0.000 description 4
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- 229910052700 potassium Inorganic materials 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
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- 229910052782 aluminium Inorganic materials 0.000 description 3
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- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- 239000011133 lead Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 229910052701 rubidium Inorganic materials 0.000 description 3
- 239000010944 silver (metal) Substances 0.000 description 3
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 2
- 229910052769 Ytterbium Inorganic materials 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
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- 238000005259 measurement Methods 0.000 description 2
- 238000010309 melting process Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
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- 229910052717 sulfur Inorganic materials 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910005900 GeTe Inorganic materials 0.000 description 1
- 229910002665 PbTe Inorganic materials 0.000 description 1
- 230000005679 Peltier effect Effects 0.000 description 1
- 230000005678 Seebeck effect Effects 0.000 description 1
- 230000005680 Thomson effect Effects 0.000 description 1
- 229910007657 ZnSb Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- WPYVAWXEWQSOGY-UHFFFAOYSA-N indium antimonide Chemical compound [Sb]#[In] WPYVAWXEWQSOGY-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- OCGWQDWYSQAFTO-UHFFFAOYSA-N tellanylidenelead Chemical compound [Pb]=[Te] OCGWQDWYSQAFTO-UHFFFAOYSA-N 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- 230000005619 thermoelectricity Effects 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
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Abstract
本發明有關於一種熱電合金及其製作方法。此熱電合金之製作方法係先提供起始材料,並對起始材料進行氧化製程,以獲得氧化材料組成物。然後,將氧化材料組成物與滲碳劑加入石英管中,並進行封管製程。接著,對封閉之石英管進行滲碳製程,即可製得具有良好熱電優值之熱電合金。
Description
本發明係有關一種熱電合金,特別是提供一種具有高熱電優值之熱電合金及其製作方法。
熱電材料可有效地直接轉換熱能與電能。依據其轉換機制之差異,熱電材料之熱電現象可為塞貝克效應(Seebeck effect)、帕爾帖效應(Peltier effect)或湯姆森效應(Thomson effect)。其中,當熱電材料之材料兩端具有溫度差或電壓差時,材料兩端會相應產生電壓差,或者形成一端吸熱一端放熱之現象。
據此,藉由前述之熱電現象,熱電材料一般可應用於廢熱回收發電(waste heat recovery)或熱電致冷(thermoelectric cooler)。
其次,熱電材料之熱電現象係取決於材料之熱電優值(thermoelectric figure-of-merit),且熱電優值係以下式(I)來表示。
其中,zT代表熱電優值;S代表Seekbeck係數;ρ代表電阻率;S 2 /ρ代表材料之功率因子(power factor);κ代表熱傳導係數;且T為絕對溫度(K)。
當熱電優值越高時,熱電材料之熱電轉換效率係越好。然而,目前商業化之熱電材料的熱電優值約為1.0,故一般之熱電材料仍無法取代用來散熱之壓縮機(熱電優值約為3.5),而侷限其應用範圍。
有鑑於此,亟須提供一種熱電合金及其製作方法,以改進習知熱電合金的缺陷。
因此,本發明之一態樣是在提供一種熱電合金之製作方法,其藉由滲碳製程所施加之高溫,使滲碳劑分解產生活性碳原子,且活性碳原子可滲入熔融之熱電合金材料中,而可提升所製得熱電合金之熱電性質。
本發明之另一態樣是在提供一種熱電合金,其係藉由前述之方法所製得。
本發明之又一態樣是在提供一種熱電合金複合物,其包含前述之熱電合金。
根據本發明之一態樣,提出一種熱電合金之製作方法。此製作方法係先提供起始材料,並進行氧化製程,以製得氧化材料組成物。其中,基於氧化材料組成物為100
原子百分比,氧化材料組成物之氧含量係0.001原子百分比至10原子百分比。然後,將氧化材料組成物與滲碳劑加入石英管中,並進行封管製程,以製得封閉石英管。接著,對封閉石英管進行滲碳製程,即可製得本發明之熱電合金。
依據本發明之一實施例,前述之起始材料包含鍺、碲、鉍、鋅、鍗、硒、銅、銦、鎵、銀、鈷、鐵及/或鉛。
依據本發明之另一實施例,前述之滲碳劑包含固體碳源、液體碳源、氣體碳源及/或電漿碳源。
依據本發明之又一實施例,前述將氧化材料組成物與滲碳劑加入石英管中之操作包含利用滲碳劑進行鍍碳製程,以於石英管之內壁形成碳膜,並加入氧化材料組成物至具有碳膜的石英管中。
依據本發明之再一實施例,前述封閉石英管之真空度不大於0.03mbar。
依據本發明之又另一實施例,前述之滲碳製程包含升溫步驟,且升溫步驟係由200℃升溫至起始材料之熔點。
依據本發明之再另一實施例,前述滲碳製程之冷卻速率為2℃/小時至10℃/小時。
依據本發明之更另一實施例,於進行前述之滲碳製程後,此製作方法更進一步對熱電合金進行長晶製程。
根據本發明之另一態樣,提出一種熱電合金,其係藉由前述之方法所製得。其中,基於熱電合金為100重
量百分比,熱電合金之碳含量為0.005重量百分比至0.05重量百分比。
依據本發明之一實施例,前述之熱電合金包含P型熱電合金與N型熱電合金。
根據本發明之又一態樣,提出一種熱電合金複合物,其包含前述之熱電合金。其中,基於熱電合金複合物之含量為100重量百分比,熱電合金之含量不小於10重量百分比。
應用本發明之熱電合金及其製作方法,其藉由進行滲碳製程,使所加入之滲碳劑分解產生活性碳原子,而可促使活性碳原子滲入熔融之氧化材料組成物中,進而提升所製得熱電合金之熱電性質。
100‧‧‧方法
110/120/130/140/150‧‧‧步驟
為了對本發明之實施例及其優點有更完整之理解,現請參照以下之說明並配合相應之圖式。必須強調的是,各種特徵並非依比例描繪且僅係為了圖解目的。相關圖式內容說明如下:〔圖1〕係繪示依照本發明之一實施例之熱電合金之製作方法的流程圖。
〔圖2A〕係繪示依照本發明之實施例1與比較例1之熱電合金的熱電優值對溫度之折線圖。
〔圖2B〕係繪示依照本發明之實施例2與比較例2之熱電合金的熱電優值對溫度之折線圖。
以下仔細討論本發明實施例之製造和使用。然而,可以理解的是,實施例提供許多可應用的發明概念,其可實施於各式各樣的特定內容中。所討論之特定實施例僅供說明,並非用以限定本發明之範圍。
一般而言,熱電合金中之雜質元素的含量越少時,熱電合金之電阻值越低,故其熱電優值越高,而具有較佳之熱電性質。據此,為降低其他雜質元素對熱電性質的影響,熱電合金所選用之起始材料均係選用高純度之材料,或係藉由一系列之純化製程來處理起始材料,以去除其中之雜質元素。舉例而言,當熱電合金之氧原子含量越高時,熱電合金之電阻值越高,故其熱電性質越差。據此,起始材料之純度要求係嚴苛的。再者,為避免起始材料於儲放時被氧化,起始材料均須妥善保存。然而,一般熱電合金之熱電優值仍未有顯著之進步。
據此,為有效提升熱電合金之熱電優值,本發明藉由先對熱電合金之起始材料進行氧化,以增加起始材料之氧含量,並進一步進行滲碳製程,以藉由還原氧化後之起始材料來提升碳滲入所製得之熱電合金中的含量,進而降低其熱傳導係數且增加功率因子,因此提升本發明熱電合金之熱電性質。
請參照圖1,其係繪示依照本發明之一實施例之熱電合金之製作方法的流程圖。方法100係先提供起始材
料,並對起始材料進行氧化製程,以製得氧化材料組成物,如步驟110與步驟120所示。依據所欲製得之熱電合金的化學組成,起始材料具有相應之組成與比例。在一些實施例中,起始材料為一混合物。在此些實施例中,此混合物可包含金屬材料及/或非金屬材料。在一些實施例中,起始材料可包含但不限於鍺、碲、鉍、鋅、鍗、硒、銅、銦、鎵、銀、鈷、鐵、鉛、其他適當之熱電材料,或上述材料之任意混合。在一些實施例中,為製得具有良好性質之熱電合金,起始材料中之各材料的純度較佳不小於4N。
基於步驟120所製得之氧化材料組成物為100原子百分比,氧化材料組成物的氧含量可為0.001原子百分比至10原子百分比。在一些實施例中,氧化材料組成物的氧含量較佳可為1原子百分比至6原子百分比,且更佳為2原子百分比至5原子百分比。
然後,將氧化材料組成物與滲碳劑加入石英管中,並進行封管製程,以製得封閉石英管,如步驟130所示。在一些實施例中,所加入之滲碳劑並沒有特別之限制,其僅須可於後續之滲碳製程作為碳源即可。在一些實施例中,滲碳劑之主要組成為碳原子,且其較佳不包含其他雜質元素,以避免所製得熱電合金之組成無法滿足需求。在一些實施例中,滲碳劑可包含但不限於固體碳源、液體碳源、氣體碳源、電漿碳源、其他適當型態之碳源,或上述材料之任意混合。舉例而言,滲碳劑可包含但不限於碳粉、石墨粉、石墨烯、
鑽石、碳奈米管、無定型碳、富勒烯、其他適當之材料,或上述材料之任意混合。
在一些實施例中,滲碳劑可與氧化材料組成物同時加入石英管中。在其他實施例中,滲碳劑可於加入氧化材料組成物之前,預先形成於石英管中,或者加至石英管中。舉例而言,石英管可先進行鍍碳製程,以預先使滲碳劑形成於石英管內壁上,而形成內壁具有碳膜之石英管。然後,氧化材料組成物即可加入至具有碳膜之石英管中,並進行接續之封管製程。
當進行封管製程時,利用抽氣泵浦抽去石英管中之空氣,並利用氧氣-瓦斯火焰槍燒熔石英管之管口,以封閉石英管。其中,封閉石英管中之真空度不大於0.03mbar。
進行封管製程後,對所獲得之封閉石英管進行滲碳製程,即可製得本發明之熱電合金,如步驟140與步驟150所示。當進行滲碳製程時,封閉石英管中之滲碳劑(或碳原子)可還原氧化材料組成物,且隨著滲碳製程之進行,活性碳原子可滲入熔融之氧化材料組成物中,而可提升所製得熱電合金之性質。在一些實施例中,基於所製得之熱電合金為100重量百分比,熱電合金之碳含量可為0.005重量百分比至0.05重量百分比。在一些實施例中,所製得之熱電合金較佳不包含氧原子。若熱電合金包含氧原子時,熱電合金之電阻值將上升,而降低其熱電優值。
為促使滲碳劑分解出活性碳原子,並使活性碳原子有效地滲入熱電合金中,滲碳製程包含升溫步驟,且升溫步驟係由200℃升溫至前述起始材料之熔點,以使碳原子滲入氧化材料組成物中,並熔融氧化材料組成物。其中,升溫步驟係升溫至所有氧化材料組成物均可熔融為佳。換言之,於升溫至設定溫度時,氧化材料組成物均被熔融。在一些實施例中,升溫步驟較佳係由200℃升溫至1100℃,且更佳為由200℃升溫至950℃。在一些實施例中,當進行滲碳製程時,加熱爐係先由室溫加熱至200℃,再將封閉石英管放置至200℃之加熱爐中。在一些實施例中,於滲碳製程之升溫階段的期間,碳原子可先滲入氧化材料組成物中,以還原氧化材料組成物。接著,被還原之氧化材料組成物可熔融結合為液態之熱電合金。在一些實施例中,於滲碳製程之升溫階段的期間,氧化材料組成物可先熔融為液體,且碳原子滲入還原此些液態之氧化材料組成物。接著,被還原之氧化材料組成物結合為熱電合金。在一些實施例中,於滲碳製程之升溫階段的期間,氧化材料組成物可先熔融結合為液態之熱電合金。然後,碳原子可滲入液態之熱電合金,並還原其中之氧原子。
於滲碳製程中,若前述所製得氧化材料組成物之氧含量小於0.001原子百分比時,由於氧化材料組成物之氧化程度過低,故受熱所分解之活性碳原子不易滲入熱電合金中,而降低熱電合金之碳含量,因此降低所製得熱電合金之熱電性質。若氧化材料組成物之氧含量大於10原子百分
比時,部分之氧化材料將無法被還原,而使所製得之熱電材料仍含有氧原子,進而提升熱電材料之電阻值,因此降低其熱電性質。
另外,於滲碳製程中,當封閉石英管之真空度為前述之範圍時,封閉石英管之內部可為低氧環境。故,滲碳製程所產生之活性碳原子可更有效地還原氧化材料組成物,並滲入熔融之氧化材料組成物中,而不被環境中之氧原子所干擾,進而降低所製得熱電合金之熱傳導係數且增加功率因子。因此,所製得之熱電合金具有較佳之熱電性質。
當高溫之滲碳製程進行完畢後,滲碳製程之冷卻速率可為2℃/小時至10℃/小時。當冷卻速率為前述之範圍時,熔融之被還原的氧化材料組成物可緩慢冷卻,而具有較緻密之結構與較佳之結晶性質,進而提升所製得熱電合金之性質。在一些實施例中,滲碳製程之冷卻速率較佳可為3℃/小時至8℃/小時,且更佳可為5℃/小時至7℃/小時。
於進行前述之滲碳製程後,此製作方法可選擇性地對所獲得之熱電合金進行長晶製程,而可進一步提升所製得熱電合金之結晶性質,因此提升長晶製程所製得熱電合金塊材的熱電性質。
在一具體例中,依據所選用之起始材料的用量與組成,利用前述方法所製得之熱電合金可為P型熱電合金與N型熱電合金。
在一些具體例中,所製得之熱電合金可具有M1x1(B1y1C1z1)之組成。其中,M1代表摻雜之金屬元素,
且M1可代表Li、Na、K、Rb、Cs、Be、Mg、Ca、Sr、Ba、Cu、Ag、Au、Zn、Mn、Fe、Co、Ni、La、Ce、Pr、Nd、Yb、其他適當之元素,或上述元素之任意混合;B1可代表Al、Ga、In、Sb、Bi、其他適當之元素,或上述元素之任意混合;C1可代表O、S、Se、Te、F、Cl、Br、I、其他適當之元素,或上述元素之任意混合;x1代表大於0且小於1之數值;y1代表大於1.5且小於2.5之數值;z1代表大於2.3且小於3.7之數值。此種熱電合金可例如為以M1摻雜之Bi2Te3。
在一些具體例中,所製得之熱電合金可具有M2x2(B2y2C2z2)之組成。其中,M2代表摻雜之金屬元素,且可代表Li、Na、K、Rb、Sr、Mg、Ca、Sr、Ba、Cu、Ag、Au、Zn、Al、Ga、In、As、Sb、Bi、Br、I、其他適當之元素,或上述元素之任意混合;B2可代表Si、Ge、Sn、Pb、其他適當之元素,或上述元素之任意混合;C2可代表N、P、As、Sb、Bi、Te、其他適當之元素,或上述元素之任意混合;x2代表大於0.02且小於0.2之數值;y2可代表大於0.7且小於1.3之數值;z2可代表大於0.7且小於1.3之數值。此種熱電合金可例如為以M2摻雜之PbTe或GeTe。
在一些具體例中,所製得之熱電合金可具有M3x3(B3y3C3z3)之組成。其中,M3代表摻雜之金屬元素,且可代表Li、Na、K、Cs、Mg、Ca、Sr、Ba、Cu、Ag、Au、Zn、La、Ce、Mn、Fe、Co、Ni、其他適當之元素,
或上述元素之任意混合;B3可代表Al、Ga、In、Zn、Cd、其他適當之元素,或上述元素之任意混合;C3可代表N、P、As、Sb、Bi、Se、其他適當之元素,或上述元素之任意混合;x3代表大於0且小於0.5之數值;y3代表大於2.7且小於4.4之數值;z3代表大於2.5且小於3.5之數值。此種熱電合金可例如為以M3摻雜之ZnSb、Zn4Sb3、In4Se3或InSb。
在一些具體例中,所製得之熱電合金可具有M4x4(B4y4C4z4)之組成。其中,M4代表摻雜之金屬元素,且可代表Li、Cs、Rb、Ba、Ga、In、Tl、La、Ce、Pr、Nd、Yb、其他適當之元素,或上述元素之任意混合;B4可代表Fe、Co、Ni、Ru、Rh、Pd、其他適當之元素,或上述元素之任意混合;C4可代表As、Sb、其他適當之元素,或上述元素之任意混合;x4代表大於0且小於0.4之數值;y4代表大於0.7且小於1.3之數值;z4代表大於2.5且小於3.5之數值。此種熱電合金可例如為以M4摻雜之FeCoSb3。
在一些具體例中,所製得之熱電合金可具有M5x5(A5p5B5y5C5z5)之組成。其中,M5代表摻雜之金屬元素,且可代表Li、Na、K、Cs、Cl、Br、I、其他適當之元素,或上述元素之任意混合;A5可代表Cu、Ag、Au、其他適當之元素,或上述元素之任意混合;B5可代表Ga、In、Ge、Sn、As、Sb、Bi、其他適當之元素,或上述元素之任意混合;C5可代表S、Se、Te、其他適當之元素,或上述元素之任意混合;x5代表大於0且小於0.2之數值;p5代表大於0.7且小於1.3之數值;y5代表大於0.7且小於1.3
之數值;z5代表大於1.7且小於2.3之數值。此種熱電合金可例如為以M5摻雜之AgSbTe2或CuInSe2。
在一些具體例中,本發明所製得之熱電合金可與一般熱電合金混合,而形成熱電合金複合物,且此熱電合金複合物即可具有良好之熱電優值。其中,基於熱電合金複合物為100重量百分比,本發明所製得之熱電合金的含量係不小於10重量百分比,較佳為10重量百分比至80重量百分比,且更佳為50重量百分比至60重量百分比。
於進行前述之滲碳製程時,由於受熱分解之活性碳原子可滲入熔融之氧化材料組成物中,而降低所製得熱電合金之熱傳導係數,或增加其功率因子(power factor),因此所製得之熱電合金具有較佳之熱電性質。
以下利用實施例以說明本發明之應用,然其並非用以限定本發明,任何熟習此技藝者,在不脫離本發明之精神和範圍內,當可作各種之更動與潤飾。
首先,提供純度為4N以上之銅金屬(Cu)、鉍金屬(Bi)與碲金屬(Te),並對此些金屬進行氧化製程,以分別製得包含氧化銅、氧化鉍與氧化碲之氧化材料組成物,其中氧化材料組成物的氧含量為4原子百分比。然後,進行鍍碳製程,即可於石英管內壁形成碳膜。接著,將前述之氧化材
料組成物放入內壁具有碳膜之石英管中,並利用抽氣泵浦抽氣,以降低石英管之真空度。
待石英管之真空度不大於0.03mbar時,對石英管進行封管製程,以形成封閉石英管。接著,以2℃/分鐘至5℃/分鐘之升溫速率加熱封閉石英管,直至封閉石英管之溫度為950℃,以使碳膜可受熱產生活性碳原子,而可進行滲碳製程。
待石英管內之材料均勻化後,冷卻至室溫,並將凝固樣品放入長晶爐中,以4℃/小時之速度進行長晶,即可製得實施例1之熱電合金。所得之熱電合金以下述熱電優值之評價方式進行評價,其評價結果容後再述。
首先,提供純度為4N以上之銻金屬(Sb)、鍺金屬(Ge)與碲金屬(Te),並對此些金屬進行氧化製程,以分別製得包含氧化銻、氧化鍺與氧化碲之氧化材料組成物,其中氧化材料組成物的氧含量為10原子百分比。然後,進行鍍碳製程,即可於石英管內壁形成碳膜。接著,將前述之氧化材料組成物放入內壁具有碳膜之石英管中,並利用抽氣泵浦抽氣,以降低石英管之真空度。
待石英管之真空度不大於0.03mbar時,對石英管進行封管製程,以形成封閉石英管。接著,以2℃/分鐘至5℃/分鐘之升溫速率加熱封閉石英管,直至封閉石英管之溫度為950℃,以使碳膜可受熱產生活性碳原子,而可進行滲碳製程。
待石英管內之材料均勻化後,以5℃/小時至10℃/小時之冷卻速率降溫至室溫,即可製得實施例2之熱電合金。所得之熱電合金以下述熱電優值之評價方式進行評價,其評價結果容後再述。
比較例1之熱電合金係使用與實施例1之熱電合金的起始材料相同之組成含量。然而,比較例1係直接將此些起始材料放入石英管中,並進行封管製程,以獲得封閉石英管。
接著,對封閉石英管進行熔融製程。待石英管內之材料均勻化後,冷卻至室溫,並將凝固樣品放入長晶爐中,以4℃/小時之速度進行長晶,即可製得比較例1之熱電合金。所得之熱電合金以下述熱電優值之評價方式進行評價,其評價結果容後再述。
比較例2之熱電合金係使用與實施例2之熱電合金的起始材料相同之組成含量。然而,比較例2係直接將此些起始材料放入石英管中,並進行封管製程,以獲得封閉石英管。
接著,對封閉石英管進行熔融製程。待石英管內之材料均勻化後,以5℃/小時至10℃/小時之冷卻速率降溫至室溫,即可製得比較例2之熱電合金。所得之熱電合金以下述熱電優值之評價方式進行評價,其評價結果容後再述。
實施例1至2與比較例1至2所製得之熱電合金分別係利用賽貝克係數與電導率變溫量測系統(ULVAC-RIKO製造,且其型號為ZEM-3之量測系統)量測電阻率(ρ)與賽貝克(Seekbeck)係數(S)。於此量測系統中,利用兩鎳製電極來固定熱電合金之試片,並設置兩根熱電耦,以量測試片之溫差,其中溫差值分別設定為7K、10K、13K與16K。然後,將量測腔體之壓力降低至10-2torr,並通入6N之惰性氣體。反覆進行數次後,通入微量之高純度氦氣,以避免試片於高溫產生氧化反應。接著,將試驗電壓設定為固定值,並依據試片電阻調整試驗電流,即可藉由電腦軟體計算測得電阻率(ρ)與賽貝克係數(S),其中試驗電流之最大值為130mA。
然後,利用閃光法熱傳導儀(Netzsch製作,且其型號為LFA 457)量測熱電合金之熱傳導係數(κ)。於熱傳導儀中,以雷射光加熱熱電合金之試片的一側,並利用紅外線感測器(或熱電耦)量測試片之另一側的溫度。因此,試片於特定時間內的溫度變化可被測得。其中,熱電合金之試片係直徑為7毫米,且厚度為1.5毫米至2毫米的圓餅試片。然後,以下式(II)計算獲得實施例1至2及比較例1至2之熱電合金的熱傳導係數(κ):
κ=DC p d (II)
依據前述所測得之電阻率(ρ)、賽貝克係數(S)與熱傳導係數(κ),實施例1至2與比較例1至2之熱電合金於各溫度下的熱電優值可藉由前述之式(I)計算獲得。
請參照圖2A與圖2B,其中圖2A係繪示依照本發明之實施例1與比較例1之熱電合金的熱電優值對溫度之折線圖,且圖2B係繪示依照本發明之實施例2與比較例2之熱電合金的熱電優值對溫度之折線圖。
依據圖2A所繪示之內容可知,於300K(約為26.85℃)時,實施例1所製得之熱電合金的熱電優值為1.7,且比較例1之熱電合金的熱電優值僅為1.2。其次,於各個量測溫度下,實施例1所製得之熱電合金均具有較高之熱電優值。
另外,相較於商用之熱電合金(n型Bi摻雜之TeSe熱電材料,且其熱電優值約為0.85至1.04),於300K時,實施例1之熱電合金的熱電優值約為其2倍。
依據圖2B所繪示之內容可知,於723K(約為449.85℃)時,實施例2所製得之熱電合金的熱電優值為
2.5,且比較例2之熱電合金的熱電優值約為1.0。相同地,於各個量測溫度下,相較於比較例2所製得之熱電合金,實施例2之熱電合金均具有較高之熱電優值。
故,依據實施例1至實施例2與比較例1至比較例2之評價結果可知,本案之製作方法藉由氧化製程,使所使用之起始材料形成氧化態,而可於後續之滲碳製程被所產生之活性碳原子所還原,並使此些活性碳原子滲入熔融之氧化材料組成物中,進而降低所製得熱電合金之熱傳導係數且增加其功率因子,因此可提升熱電合金之熱電性質。
雖然本發明已以實施方式揭露如上,然其並非用以限定本發明,在本發明所屬技術領域中任何具有通常知識者,在不脫離本發明之精神和範圍內,當可作各種之更動與潤飾,因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。
100‧‧‧方法
110/120/130/140/150‧‧‧步驟
Claims (10)
- 一種熱電合金之製作方法,包含:提供一起始材料,其中該起始材料包含鍺、碲、鉍、鋅、鍗、硒、銅、銦、鎵、銀、鈷、鐵及/或鉛;對該起始材料進行氧化製程,以製得氧化材料組成物,其中基於該氧化材料組成物為100原子百分比,該氧化材料組成物之氧含量係0.001原子百分比至10原子百分比;將該氧化材料組成物與一滲碳劑加入一石英管中,並進行一封管製程,以製得一封閉石英管;以及對該封閉石英管進行一滲碳製程,以製得該熱電合金。
- 如申請專利範圍第1項所述之熱電合金之製作方法,其中該滲碳劑包含一固體碳源、一液體碳源、一氣體碳源及/或一電漿碳源。
- 如申請專利範圍第1項所述之熱電合金之製作方法,其中將該氧化材料組成物與該滲碳劑加入該石英管中之操作包含:利用該滲碳劑進行一鍍碳製程,以於該石英管之一內壁形成一碳膜;以及加入該氧化材料組成物至具有該碳膜的該石英管中。
- 如申請專利範圍第1項所述之熱電合金之製作方法,其中該封閉石英管之一真空度不大於0.03mbar。
- 如申請專利範圍第1項所述之熱電合金之製作方法,其中該滲碳製程包含一升溫步驟,且該升溫步驟係由200℃升溫至該起始材料之熔點。
- 如申請專利範圍第5項所述之熱電合金之製作方法,其中該滲碳製程之一冷卻速率為2℃/小時至10℃/小時。
- 如申請專利範圍第1項所述之熱電合金之製作方法,於進行該滲碳製程後,該製作方法更包含:對該熱電合金進行一長晶製程。
- 一種熱電合金,藉由如申請專利範圍第1至7項中之任一項所述之方法所製得,其中基於該熱電合金為100重量百分比,該熱電合金之碳含量為0.005重量百分比至0.05重量百分比。
- 如申請專利範圍第8項所述之熱電合金,其中該熱電合金包含P型熱電合金與N型熱電合金。
- 一種熱電合金複合物,包含:如申請專利範圍第8或9項所述之熱電合金,其中基於該熱電合金複合物之含量為100重量百分比,該熱電合金之含量不小於10重量百分比。
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CN106997919A (zh) * | 2017-03-06 | 2017-08-01 | 宁波工程学院 | n‑型Cu4In9Se16基中高温热电半导体及其合成工艺 |
CN107010609B (zh) * | 2017-03-10 | 2019-01-04 | 宁波工程学院 | 一种p-型Cu4Ga6Te11基中温热电半导体 |
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2018
- 2018-10-18 TW TW107136813A patent/TWI683910B/zh active
- 2018-12-17 CN CN201811540147.4A patent/CN111081859B/zh active Active
- 2018-12-18 EP EP18213379.3A patent/EP3640361B1/en active Active
- 2018-12-19 JP JP2018237243A patent/JP2020065035A/ja active Pending
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EP3640361B1 (en) | 2023-03-01 |
TWI683910B (zh) | 2020-02-01 |
US20200123637A1 (en) | 2020-04-23 |
JP2020065035A (ja) | 2020-04-23 |
US10975456B2 (en) | 2021-04-13 |
CN111081859A (zh) | 2020-04-28 |
CN111081859B (zh) | 2022-03-22 |
EP3640361A1 (en) | 2020-04-22 |
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