WO2018038285A1 - Élément thermoélectrique et module thermoélectrique comprenant celui-ci - Google Patents

Élément thermoélectrique et module thermoélectrique comprenant celui-ci Download PDF

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Publication number
WO2018038285A1
WO2018038285A1 PCT/KR2016/009362 KR2016009362W WO2018038285A1 WO 2018038285 A1 WO2018038285 A1 WO 2018038285A1 KR 2016009362 W KR2016009362 W KR 2016009362W WO 2018038285 A1 WO2018038285 A1 WO 2018038285A1
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WO
WIPO (PCT)
Prior art keywords
thermoelectric
thermoelectric element
substrate
diffusion barrier
barrier layer
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Application number
PCT/KR2016/009362
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English (en)
Korean (ko)
Inventor
김종배
연병훈
최종일
황병진
손경현
박재성
양승호
박주현
Original Assignee
희성금속 주식회사
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Application filed by 희성금속 주식회사 filed Critical 희성금속 주식회사
Publication of WO2018038285A1 publication Critical patent/WO2018038285A1/fr

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Classifications

    • 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
    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02N—ELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
    • H02N11/00—Generators or motors not provided for elsewhere; Alleged perpetua mobilia obtained by electric or magnetic means
    • 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
    • H10N10/10—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects
    • 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
    • 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 element and thermoelectrics including the same
  • the present invention relates to a thermoelectric element and thermoelectrics including the same.
  • thermoelectric elements are various devices using the Peltier effect and the Seebeck effect, which are the interactions between heat and electricity, and are applied to thermoelectric power generation such as waste heat generation and active sensing.
  • thermoelectric elements are bonded to the electrodes through soldering or bridging.
  • the electrode mainly uses a Cu electrode, in the case of the Cu electrode, the Cu component penetrates into the thermoelectric element during soldering. As a result, the thermoelectric performance of the thermoelectric element is lowered, or the infiltrated Cu forms an intermetallic compound with the components of the thermoelectric element, thereby deteriorating mechanical properties.
  • thermoelectric device having a Ni plating layer formed on a surface thereof was developed.
  • the conventional thermoelectric element when the Ni plating layer is as thin as about 0.3 to 3 urn, it is difficult to perform the role of diffusion prevention.
  • the conventional thermoelectric element has a thick Ni plating layer formed at a level of about 20 to 40 im. As a result, the resistance of the thermoelectric element is increased to decrease the output value of the thermoelectric elements.
  • the bonding stability at high temperature is still lowered.
  • thermoelectric performance According to the bonding stability and thickness at high temperature Development of thermoelectric elements is necessary.
  • An object of the present invention is to provide a thermoelectric device excellent in thermal stability and bonding stability at high temperature and excellent in thermoelectric performance.
  • Another object of the present invention is to provide thermal elements having a high temperature use temperature band including the thermal element.
  • the present invention is a bulk type thermoelectric semiconductor substrate; And a diffusion barrier layer formed on at least one of tantalum (Ta), tungsten (W), molybdenum (Mo), and titanium (Ti) on the surface of the bulk thermal semiconductor substrate. .
  • the bulk type thermoelectric substrate preferably has a surface roughness Ra of 0.5 to 3.0 urn.
  • the diffusion barrier layer preferably has a thickness in the range of 0.3 to 20 urn. It is preferable that such a thermoelectric element is dedicated to thermo development.
  • thermoelectrics including the aforementioned thermoelectric elements.
  • thermoelectric device of the present invention includes a diffusion barrier layer formed of at least one selected from the group consisting of tantalum (Ta), tungsten (W), molybdenum (Mo), and titanium (Ti), and has a thermoelectric performance similar to that of a conventional thermoelectric device. Higher than conventional thermoelectric elements It is excellent in thermal stability and bonding stability at temperature. Therefore, the thermoelectrics including the thermoelectric device of the present invention can be used at a higher temperature range than the conventional thermoelectrics, and further improve the power generation output.
  • thermoelectric device 1 is a cross-sectional view showing a thermoelectric device according to an example of the present invention.
  • thermoelectrics according to an example of the present invention.
  • thermoelectric device manufactured in Example 1 is a FEM scanning electron microscope (FE—SEM) photograph of the thermoelectric device manufactured in Example 1;
  • Figure 4 is a FE-SEM picture of the thermal wool prepared in Comparative Example 1, (a) is a FE-SEM picture before the heat treatment, (b) is a FE-SEM picture after the heat treatment.
  • thermoelectric element 11 bulk type thermoelectric semiconductor substrate
  • thermoelectric element 21 upper front
  • thermoelectric semiconductor substrate a metal such as tantalum (Ta), tungsten (W), molybdenum (Mo), titanium (Ti), or the like is formed on the surface of a thermoelectric semiconductor substrate, the bulk type thermoelectric substrate during high temperature bonding of the thermoelectric element and the electrode Diffusion prevention effect and bonding at high temperature It was found that the stability was excellent.
  • a metal such as tantalum (Ta), tungsten (W), molybdenum (Mo), titanium (Ti), or the like is formed on the surface of a thermoelectric semiconductor substrate, the bulk type thermoelectric substrate during high temperature bonding of the thermoelectric element and the electrode Diffusion prevention effect and bonding at high temperature It was found that the stability was excellent.
  • tantalum (Ta), tungsten (W), molybdenum (Mo), and titanium (Ti) are metals having a high melting point of about 1600 ° C. or higher, and the melting point is higher than that of electrode components (eg, Cu, Au, Ag, etc.). Since it is high, it is thermodynamically stable even at a high temperature of about 300 ° C. or higher, and the reaction rate is slow even if it does not react or reacts chemically with the electrode. Therefore, when the thermoelectric element includes a diffusion barrier layer formed of the metal, when the thermoelectric element is bonded to an electrode through soldering or brazing, the diffusion barrier layer has a thickness of about 0.3 to 5.
  • the electrode component can be prevented from diffusing into the bulk type thermoconductor substrate.
  • the thermoelectrics including the thermoelectric elements are used in silver of about 300 ° C or more, since the diffusion barrier layer is thermodynamically stable, the diffusion barrier layer is bonded between the thermoelectric semiconductor substrate and the electrode without a separate interlayer adhesion layer. The state can be kept stable.
  • the metal since the metal has excellent electrical conductivity and thermal conductivity, and has low contact resistance to an electrode (for example, Cu, etc.) or a substrate, the diffusion preventing layer is formed of heat generated from the thermoconductor substrate. It does not interfere with the movement of electricity, and therefore does not cause a decrease in thermoelectric performance of the thermoelectric element.
  • thermoelectric device is characterized in that the diffusion barrier layer formed of at least one selected from the group consisting of Ta, W, Mo and Ti is disposed on the surface of the bulk type thermoelectric semiconductor substrate.
  • thermoelectric device of the present invention has excellent thermoelectric performance similar to that of the conventional thermoelectric device, and has superior thermal stability and bonding stability at high temperature than the conventional thermoelectric device, and can further increase the use temperature range of the thermoelectric devices. Can improve their power generation output.
  • thermoelectric element 10 of the present invention includes a bulk type thermoelectric semiconductor substrate 11 and a diffusion barrier layer 12.
  • thermoconductor substrate usable in the present invention is formed of a material that generates electricity when a temperature difference is generated at both ends when electricity is applied, or a temperature difference occurs at both ends thereof, and is a material that generates electricity by a temperature difference between both ends. It is preferable. For example, it may be formed of at least one selected from the group consisting of bismuth (Bi), tellurium (Te), selenium (Se), antimony (Sb), copper (Cu), and iodine (I), but is not limited thereto. Don't.
  • thermoelectric device of the present invention including the bulk type thermoelectric semiconductor substrate can be easily applied to a thermoelectric power generation system using the Seebeck effect.
  • thermoelectric substrates are p-type bulk thermoelectric substrates or n-type bulks.
  • the thermoelectric semiconductor may be a substrate, and thus, the thermoelectric device of the present invention may be a p-type thermoelectric device or an n-type thermoelectric device.
  • the surface roughness Ra of the bulk thermoelectric substrate is not particularly limited, but in the range of about 0.5 to 3.0 urn, adhesion with the diffusion barrier layer may be improved without a defect.
  • the thickness of the said bulk type thermoconductor base material is not specifically limited. However, if the thickness of the bulk type thermoconductor substrate is too thin and the distance between the hot side and the cold side is too close, the section where the temperature deviation occurs due to interference may be too small. If the thickness of the bulk type thermoelectric semiconductor substrate is too thick so that the distance between the heat dissipation portion and the corner portion is too far, the thermoelectric element region having a temperature distribution having a high thermoelectric performance index (ZT) is relatively small and thus the efficiency may be lowered. Therefore, the thickness of the bulk type thermoelectric substrate is preferably in the range of about 1 to 5 mni.
  • thermoelectric semiconductor substrate may be formed according to a method for manufacturing a thermoelectric material known in the art.
  • the thermoconductor substrate may be prepared by dissolving the raw material powder, performing melt spinning, gas atomization, and the like followed by pressure sintering.
  • the diffusion barrier layer 12 is formed of a material selected from the group consisting of tantalum (Ta), tungsten (W), molybdenum (Mo), titanium (Ti) and alloys thereof on the surface of the thermoelectric semiconductor substrate 11. do.
  • thermoconductor base and the electrode an appropriate metal is used according to the type of the thermoconductor base and the electrode, and in terms of thermal fatigue and life characteristics, the thermoconductor base and / or the electrode It is preferable to use Ta and / or Ti as a component of the diffusion barrier layer having a small difference in coefficient of thermal expansion.
  • the diffusion barrier layer 12 can improve the adhesion (adhesiveness) of the thermoelectric element to the electrode while delaying or preventing the mutual diffusion between the thermoelectric semiconductor substrate and the electrode.
  • the thickness of the diffusion barrier layer is not particularly limited, but is preferably adjusted in consideration of the thermoelectric performance index (ZT) according to the type of the thermoelectric semiconductor substrate.
  • ZT thermoelectric performance index
  • the thickness of the diffusion barrier layer is about 0. In the range from 3 to 20, preferably about 0.
  • the output value of the thermoelectric films can be improved, which is preferable.
  • Such a diffusion barrier layer may be formed according to a thin film formation method known in the art.
  • Physical vapor deposition such as, for example, sputter deposition, thermal evaporation vacuum deposition, etc .
  • Chemical vapor deposition such as atmospheric chemical vapor deposition, low pressure chemical vapor deposition, plasma chemical vapor deposition, and the like; There is a plating method and the like, but is not limited thereto.
  • the diffusion barrier layer is preferably formed on the bulk type thermoelectric substrate in the form of a thin film by sputter deposition.
  • the sputtering deposition conditions are not particularly limited, but Si P l at e may be used as the substrate, argon (Ar), etc. may be used as the process gas, and the vacuum degree is about
  • thermoelectric element 0.5 to 2 Pa range
  • the applied voltage ranges from about 800 to 1200 W
  • the temperature is at room temperature, preferably in the range of about 19 ⁇ 22 ° C
  • the deposition rate may be in the range of about 7 to 15 A / sec.
  • the shape of the above-mentioned thermoelectric element is not particularly limited, and may be, for example, a rectangular parallelepiped shape.
  • thermoelectric elements that can be used in a thermoelectric angle system or a thermoelectric power generation system.
  • the thermoelectric elements include the aforementioned thermoelectric elements, and thus the power generation output can be increased because they have a high temperature use temperature band.
  • the thermoelectric elements 100 may include a p-type thermoelectric element 10a, an n-type thermoelectric element 10b, an upper electrode 21, a lower electrode 22, and an upper substrate ( 31) and a lower substrate 32, wherein at least one of the p-type thermoelectric element 10a and the n-type thermoelectric element 10b is the aforementioned thermoelectric element 10 (see FIG. 1).
  • thermoelectrics 100 the p-type thermoelectric element 10a and the n-type thermoelectric element 10b are one or plural, and they are alternately arranged in one direction to form a matrix shape.
  • the diffusion barrier layer 12 of each thermoelectric element (10a, 10b) is located at the junction of the upper electrode 21 and the lower electrode 22, between the thermoelectric semiconductor substrate 11 and the electrodes (21, 22). While preventing diffusion, the junction with the electrodes 21 and 22 can be stably maintained at high temperature. Accordingly, the thermoelectric module 100 of the present invention, as well as it could be used in at least about 300 ° C Ko Un, the power generation output can be improved.
  • the upper electrode 21 and the lower electrode 22 electrically connect the upper and lower surfaces of the p-type thermoelectric element and the 11-type thermoelectric element that are adjacent to each other in one direction.
  • These upper and lower electrodes 21, 22 are made of water such as aluminum, nickel, gold, copper, silver, and the like, respectively. It may be formed of a quality, but is not limited thereto.
  • the upper substrate 31 is disposed on the outer surface of the upper electrode 21 to generate heat (or heat absorption), and the lower substrate 32 is disposed on the outer surface of the lower electrode 22 to absorb heat (or heat generation).
  • Non-limiting examples of such substrates 31 and 32 include sapphire, silicon, quartz substrates, and the like.
  • thermoelectrics may further include a solder layer (not shown) between the thermoelectric elements 11 and 12 and the electrodes 21 and 22, or an insulating film (not shown) formed between the thermoelectric elements. It may further include).
  • thermocouples can be prepared according to conventional methods known in the art.
  • the present invention will be described in detail with reference to Examples, but the following Examples and Experimental Examples are merely illustrative of one embodiment of the present invention, and the scope of the present invention is not limited by the following Examples and Experimental Examples. .
  • Bi, Te, Sb and Se raw materials having high purity of 5N or more were prepared. At this time, Bi, Te and Sb raw materials were weighed to have a target composition of Bio. ⁇ TesSbLss for P-type thermoelectric materials, and Bi, Te and Se raw materials were Bi 2 Te2. 7 Se 0 . Each was weighed to have a target composition of 3 , and 1% of Te was further added in consideration of volatilization of Te.
  • a Ta film (thickness: 0.5) was deposited on the surface of the sintered body at an applied voltage of 1,000 W and a deposition rate of 85 A / sec using Ta Sputter, and then cut to prepare a pellet type thermoelectric device. It was.
  • thermoelectric element obtained above is shown in FIG. 3.
  • FE-SEM field emission scanning electron microscope
  • thermostyrene resin 1-2.
  • thermoelectric elements were bonded by soldering at about 300 ° C. to prepare thermoelectrics.
  • thermoelectric element and thermoelectrics were prepared in the same manner as in Example 1 except that a Ni plating film of 30 kV was formed.
  • FIG. 4 (a) is a FE-SEM photograph before heat treatment of the thermoforms, in which a Ni plating film is present at an interface between an electrode and a thermoconductor substrate, while FIG. 4 (b) shows the thermoforms at about 300 ° C.
  • the FE- SEM photograph after a heat treatment at, the electrode was in the interface between the thermoelectric semiconductor substrate Ni plating film is confirmed that almost invisible in this way eu, in the conventional thermoelectric device comprising a N i plating, Ni plating layers It can be seen that it is lost at a high temperature of about 300 ° C or more, and does not function properly as a diffusion barrier layer.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Powder Metallurgy (AREA)

Abstract

La présente invention concerne un élément thermoélectrique et un module thermoélectrique comprenant celui-ci, l'élément thermoélectrique comprenant une couche de barrière de diffusion constituée d'au moins l'un choisi dans le groupe constitué du tantale (Ta), du tungstène (W), du molybdène (Mo) et du titane (Ti).
PCT/KR2016/009362 2016-08-23 2016-08-24 Élément thermoélectrique et module thermoélectrique comprenant celui-ci WO2018038285A1 (fr)

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KR10-2016-0106796 2016-08-23
KR20160106796 2016-08-23

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WO2018038285A1 true WO2018038285A1 (fr) 2018-03-01

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Publication number Priority date Publication date Assignee Title
KR102311803B1 (ko) 2018-11-12 2021-10-08 한국전기연구원 열전소재의 확산방지층 및 이의 제조방법
KR102626845B1 (ko) * 2019-09-10 2024-01-17 주식회사 엘지화학 열전 모듈 및 그 제조 방법
KR20220115664A (ko) * 2021-02-08 2022-08-18 한국재료연구원 전기도금법으로 형성된 접합층 및 확산방지 구조를 포함하는 소자 및 이의 제조방법

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR19990067520A (ko) * 1996-12-24 1999-08-25 이마이 키요스케 열전소자및그제조방법
WO2003007391A1 (fr) * 2001-07-12 2003-01-23 Ferrotec (Usa) Corporation Module thermoelectrique a substrats de film mince
US20110023930A1 (en) * 2008-01-23 2011-02-03 Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung E.V. Method for producing a thermoelectric component and thermoelectric component
US20130032189A1 (en) * 2011-08-03 2013-02-07 Marlow Industries, Inc. High Temperature Thermoelectrics
US20130160807A1 (en) * 2010-08-23 2013-06-27 Emitec Gesellschaft Fuer Emissionstechnologie Mbh Semiconductor element for a thermoelectric module, method for producing the semiconductor element and thermoelectric module

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR19990067520A (ko) * 1996-12-24 1999-08-25 이마이 키요스케 열전소자및그제조방법
WO2003007391A1 (fr) * 2001-07-12 2003-01-23 Ferrotec (Usa) Corporation Module thermoelectrique a substrats de film mince
US20110023930A1 (en) * 2008-01-23 2011-02-03 Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung E.V. Method for producing a thermoelectric component and thermoelectric component
US20130160807A1 (en) * 2010-08-23 2013-06-27 Emitec Gesellschaft Fuer Emissionstechnologie Mbh Semiconductor element for a thermoelectric module, method for producing the semiconductor element and thermoelectric module
US20130032189A1 (en) * 2011-08-03 2013-02-07 Marlow Industries, Inc. High Temperature Thermoelectrics

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