WO2018038540A1 - Thermoelectric element and thermoelectric module comprising same - Google Patents

Thermoelectric element and thermoelectric module comprising same Download PDF

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Publication number
WO2018038540A1
WO2018038540A1 PCT/KR2017/009227 KR2017009227W WO2018038540A1 WO 2018038540 A1 WO2018038540 A1 WO 2018038540A1 KR 2017009227 W KR2017009227 W KR 2017009227W WO 2018038540 A1 WO2018038540 A1 WO 2018038540A1
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WIPO (PCT)
Prior art keywords
thermoelectric
barrier layer
diffusion barrier
thermoelectric element
substrate
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PCT/KR2017/009227
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French (fr)
Korean (ko)
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김종배
연병훈
최종일
황병진
손경현
박재성
양승호
박주현
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희성금속 주식회사
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Priority claimed from KR1020170106764A external-priority patent/KR20180022611A/en
Publication of WO2018038540A1 publication Critical patent/WO2018038540A1/en

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    • 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
    • H10N10/10—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
    • 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

Definitions

  • the present invention relates to a thermoelectric element and a thermoelectric module including the same.
  • thermoelectric elements are various devices using the Peltier effect and the Seebeck effect, which are caused by the interaction between heat and electricity, and are applied to thermoelectric generation and active cooling such as waste thermal power generation.
  • the thermoelectric element is bonded to the electrode through soldering or brazing.
  • the electrode mainly uses a Cu electrode, in the case of the Cu electrode, the Cu component or the solder component penetrates into the thermoelectric element during bonding. As a result, the thermoelectric performance of the thermoelectric element is lowered or the penetrated Cu forms an intermetallic compound with the components of the thermoelectric element, thereby causing a problem of deteriorating mechanical properties.
  • thermoelectric device in which a Ni plating layer is formed on a surface thereof has been developed.
  • the conventional thermoelectric element when the Ni plating layer is as thin as about 0.3 to 3 ⁇ m, it is difficult to faithfully perform the role of diffusion prevention.
  • the conventional thermoelectric device has a thick Ni plating layer formed at a level of about 20 to 40 ⁇ m, thereby increasing resistance and lowering the output value of the thermoelectric module.
  • the bonding stability at a high temperature is still lowered, and the thermal stability at a high temperature of 400 ° C. or more is lowered, causing a problem that Ni itself diffuses into the thermoelectric device.
  • thermoelectric device having excellent thermoelectric performance according to thermal stability, junction stability, and thickness at high temperature.
  • An object of the present invention is to provide a thermoelectric element which is excellent in thermal stability and bonding stability at high temperature and excellent in thermoelectric performance.
  • thermoelectric module 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 selected from the group consisting 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 ⁇ m range.
  • the diffusion barrier layer is preferably in the range of 0.3 to 20 ⁇ m thickness.
  • Ni nickel
  • thermoelectric element is dedicated to thermo development.
  • thermoelectric module including the above-mentioned thermoelectric element.
  • 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), thereby having a thermoelectric performance similar to that of a conventional thermoelectric device.
  • a diffusion barrier layer formed of at least one selected from the group consisting of tantalum (Ta), tungsten (W), molybdenum (Mo), and titanium (Ti), thereby having a thermoelectric performance similar to that of a conventional thermoelectric device.
  • thermal stability and bonding stability at high temperature are excellent. Therefore, the thermoelectric module including the thermoelectric device of the present invention can be used at a higher temperature range than the conventional thermoelectric module, 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.
  • thermoelectric device 2 is a cross-sectional view illustrating a thermoelectric device according to another exemplary embodiment of the present invention.
  • thermoelectric module 3 is a perspective view showing a thermoelectric module according to an example of the present invention.
  • thermoelectric module 4 is a field emission scanning electron microscope (FE-SEM) photograph showing a cross section of the thermoelectric module of Example 1 after heat treatment.
  • FE-SEM field emission scanning electron microscope
  • thermoelectric module manufactured 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 module of Example 2 is a FE-SEM photograph showing a cross section of the thermoelectric module of Example 2 after heat treatment.
  • thermoelectric module 7 is a FE-SEM photograph showing a cross section of the thermoelectric module of Comparative Example 2 subjected to heat treatment.
  • thermoelectric module 8 is a FE-SEM photograph showing a cross section of the thermoelectric module of Comparative Example 3 subjected to heat treatment.
  • thermoelectric module 9 is a graph showing the resistance change of the thermoelectric module of Example 2, Comparative Examples 2 and 3 according to the temperature change.
  • thermoelectric element thermoelectric element
  • 11 bulk type thermoelectric semiconductor substrate
  • 10a p-type thermoelectric element
  • 10b n-type thermoelectric element
  • thermoelectric module 100: thermoelectric module
  • 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 thermoconductor substrate during high temperature bonding of a thermoelectric element and an electrode It was found that the effect of preventing diffusion between the electrode and the electrode and the bonding stability at high temperature were excellent.
  • a metal such as tantalum (Ta), tungsten (W), molybdenum (Mo), titanium (Ti), or the like
  • tantalum (Ta), tungsten (W), molybdenum (Mo) and titanium (Ti) are metals having a high melting point of about 1600 ° C. or higher, and have a melting point higher than that of electrode components (eg, Cu, Au, Ag, etc.). Because of its high temperature, 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 chemically react 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 or the like through soldering or brazing, the diffusion barrier layer is thin with a thickness of about 0.3 to 5 ⁇ m.
  • thermoelectric module including the thermoelectric element Even if the electrode component, the solder component, or the like can be prevented from being diffused into the bulk type thermoelectric substrate.
  • thermoelectric module including the thermoelectric element even when the thermoelectric module including the thermoelectric element is used at a temperature of about 300 ° C. or more, since the diffusion barrier layer is thermodynamically stable, the diffusion barrier layer is stable in the bonding state between the thermoelectric semiconductor substrate and the electrode without a separate interlayer adhesive layer. Can be maintained.
  • the metal since the metal has excellent electrical conductivity and thermal conductivity, and has low contact resistivity with respect to an electrode (for example, Cu, etc.) or a substrate, the diffusion barrier layer is used to transfer heat or electricity generated from the thermoelectric substrate. Does not disturb, and thus does not cause a decrease in thermoelectric performance of the thermoelectric element.
  • tantalum (Ta) and titanium (Ti) among the components of the diffusion barrier layer have a coefficient of thermal expansion similar to that of a thermoelectric semiconductor substrate and / or an electrode. Therefore, in the case of a thermoelectric device in which the diffusion barrier layer is formed of Ta and / or Ti, the thermal fatigue rate of the diffusion barrier layer and the thermoelectric semiconductor substrate and / or the electrode is small, so that the thermal fatigue rate in use is small. Small, and thus lifespan characteristics can be improved.
  • thermoelectric device according to the present invention 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.
  • the thermoelectric device of the present invention has a thermoelectric performance similar to that of the conventional thermoelectric device, and is superior in thermal stability and bonding stability at high temperature as compared with the conventional thermoelectric device, and further increases the use temperature range of the thermoelectric module. Can improve the power output.
  • thermoelectric element 10 of the present invention includes a bulk type thermoelectric semiconductor substrate 11 and a diffusion barrier layer 12.
  • the thermoelectric element 10 of the present invention may further include a nickel (Ni) layer 13 (see FIG. 2).
  • thermoconductor substrate usable in the present invention is formed of a material that generates electricity when a temperature difference occurs 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. desirable.
  • 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.
  • the thermoconductor substrate may be a Bi-Te-Se-based thermoconductor substrate.
  • it may be a Skutterudite-based thermoelectric semiconductor substrate.
  • thermoelectric element 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.
  • the bulk thermoelectric substrate may be a p-type bulk thermoelectric substrate or an n-type bulk thermoelectric 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 ⁇ m, adhesion to 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 thermoelectric semiconductor substrate is too thin and the distance between the hot side and the cold side is too close, a section in which the temperature deviation occurs due to interference may be too small. On the other hand, if the thickness of the bulk type thermoelectric semiconductor substrate is too thick and the distance between the heat dissipation portion and the cooling portion is too long, the thermoelectric element region exhibiting 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 thermoconductor substrate is preferably in the range of about 1 to 5 mm.
  • thermoelectric semiconductor substrate may be formed according to a method for manufacturing a thermoelectric material known in the art.
  • the thermoelectric semiconductor substrate may be prepared by dissolving raw material powder, performing melt-spinning or gas atomization, and then sequentially performing 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. .
  • an appropriate metal is used according to the type of the thermoconductor substrate and the electrode, and in terms of thermal fatigue and life characteristics, Ta and / or Ti having a small difference in coefficient of thermal expansion between the thermoconductor substrate and / or the electrode are used as components of the diffusion barrier layer. It is preferable to use.
  • the diffusion barrier layer 12 may improve the adhesion (adhesiveness) of the thermoelectric element to the electrode while delaying or preventing 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 thermoconductor substrate is a Bi-Te-Se based thermoconductor substrate
  • the thickness of the diffusion barrier layer is adjusted to about 0.3 to 20 ⁇ m range, preferably about 0.5 to 3 ⁇ m range, the resistance of the diffusion barrier layer Since this decreases, the output value of the thermoelectric module 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 methods such as atmospheric chemical vapor deposition, low pressure chemical vapor deposition, plasma chemical vapor deposition, and the like;
  • plating method there is a plating method, but the present invention 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 a Si plate or the like may be used as a substrate, and argon (Ar) may be used as a process gas, and a vacuum degree is in a range of about 0.5 to 2 Pa, and an applied voltage is about 800 to 1200 W. Range, the temperature is at room temperature, preferably in the range of about 19-22 ° C., and the deposition rate may be in the range of about 7-15 ⁇ s / sec.
  • the nickel (Ni) layer 13 may be further formed on the diffusion barrier layer 12 described above.
  • the nickel layer 13 is a layer that assists the bonding force of the diffusion barrier layer, and may improve the bonding force between the solder and the thermoelectric element when the thermoelectric module is manufactured.
  • the thickness of such a nickel layer is not specifically limited.
  • the thickness of the nickel layer may be the same as or thinner than that of the nickel layer of the conventional thermoelectric element.
  • the thickness of the nickel layer may range from about 1 to 20 ⁇ m.
  • the nickel layer 13 may be formed by a formation method known in the art, for example, a plating method and the like, and is not particularly limited.
  • thermoelectric element is not particularly limited, and may be, for example, a rectangular parallelepiped shape.
  • thermoelectric module that can be used in a thermoelectric cooling system or a thermoelectric power generation system.
  • the thermoelectric module includes the above-mentioned thermoelectric element, and thus the power generation output can be increased because it has a high temperature use temperature band.
  • the thermoelectric module 100 includes 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 FIGS. 1 and 2).
  • thermoelectric module 100 the p-type thermoelectric element 10a and the n-type thermoelectric element 10b are each 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 in the junction between 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. Therefore, the thermoelectric module 100 of the present invention can be used at a high temperature of about 300 ° C. or more, and 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 n-type thermoelectric element which are adjacent in one direction, respectively.
  • the upper and lower electrodes 21 and 22 may be formed of a material such as aluminum, nickel, gold, copper, silver, and the like, 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.
  • thermoelectric module 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).
  • thermoelectric modules may be manufactured according to conventional methods known in the art.
  • Bi, Te, Sb and Se raw materials having high purity of 5N or more were prepared.
  • Bi, Te and Sb raw materials are Bi 0 .
  • Te 44 Sb 3 were each weighed so as to have the composition of the target 1 .56
  • Bi, Te and Se raw material is Bi 2 Te 2.
  • 7 Se 0 .3 target composition were each weighed so as to have a, Te was added to the 1 wt% more in consideration of the evaporation of Te.
  • each material was charged into a quartz tube (Quartz ampoule), the quartz tube was sealed in a vacuum state at a vacuum degree of about 10 -2 Torr, and the vacuum-sealed quartz tube was charged into a Knocking Furnace, and then at about 1033 K.
  • a master alloy ingot was prepared by stirring and dissolving at a rate of 10 times / min for 2 hours and then air cooling. The master alloy ingot was then sprayed using melt spinning equipment at a copper wheel rotation speed of about 1000 rpm and an injection pressure of about 0.5 MPa to produce a metal ribbon. Thereafter, the formed metal ribbon was pressed and sintered at a sintering pressure of about 40 MPa at about 480 ° C.
  • a sintered body (diameter: ⁇ 50, thickness: 15 mm). Prepared. Thereafter, the sintered body was sliced (thickness: 5 mm), and then the surface roughness Ra of the sintered body was adjusted to about 1.4 ⁇ m. Subsequently, a Ta film (thickness: 0.5 ⁇ m) was deposited on the surface of the sintered body at an applied voltage of 1,000 W and a deposition rate of 7.85 ⁇ / sec using Ta Sputter, followed by dicing to pellet-type thermoelectric element. was prepared.
  • SPS spark plasma sintering
  • thermoelectric module A p-type thermoelectric element and an n-type thermoelectric element respectively manufactured in Example 1-1 were bonded between the first Cu electrode and the second Cu electrode by soldering at about 300 ° C. to prepare a thermoelectric module.
  • thermoelectric element and a thermoelectric module were formed in the same manner as in Example 1 except that a Ni plating film having a thickness of about 30 ⁇ m was formed instead of forming a Ta deposition film on the surface of the sintered body in Example 1-1. Prepared.
  • thermoelectric module was heat-treated at 300 °C, and then the cross-section of the thermoelectric module was shown by using an electric field scanning scanning microscope. FE-SEM images are shown in FIGS. 4 and 5, respectively.
  • thermoelectric module of Example 1 a Ta deposited film was present on the surface of the sintered body which is a thermoelectric semiconductor substrate even after the heat treatment at 300 ° C.
  • the Ni plated film existed at the interface between the Cu electrode and the sintered body before the heat treatment, but the Ni plated film was hardly visible at the boundary between the Cu electrode and the sintered body, and the distribution of the Cu electrode was widened. I could confirm it. It was estimated that Ni in the Ni plated film was diffused into the sintered body at a high temperature of about 300 ° C. or more and lost.
  • thermoelectric module using the thermoelectric device including the diffusion barrier layer according to the present invention has excellent high temperature stability.
  • thermoelectric elements 2-1. Fabrication of high temperature thermoelectric elements
  • the surface roughness of the sintered body was adjusted to about 1.5 ⁇ m.
  • a Ta film (thickness: 0.5 ⁇ m) was deposited on both surfaces of the CoSb 3 sintered body at an applied voltage of 1,000 W and a deposition rate of 7.85 ⁇ s / sec using a sputter, and then Ni plating was performed to carry out Ni plating. (Thickness: 5 mu m) was formed. Then, dicing (Dicing) to produce a thermoelectric device of the pellet type.
  • thermoelectric modules
  • thermoelectric module After brazing the copper side surface of the first DBC substrate and one surface of the thermoelectric element manufactured in Example 2-1, soldering the other side of the thermoelectric element and the copper side surface of the second DBC substrate To prepare a thermoelectric module.
  • thermoelectric device and a thermoelectric module were manufactured in the same manner as in Example 2, except that a Ta plating film was not formed on the surface of the CoSb 3 sintered body in Example 2-1, and the Ni plating layer was formed to a thickness of about 5 ⁇ m. .
  • thermoelectric device and a thermoelectric module were manufactured in the same manner as in Example 2, except that a Ta deposition film and a Ni plating layer were not formed on the surface of the CoSb 3 sintered body in Example 2-1.
  • thermoelectric modules manufactured in Example 2 were heat-treated at 400 ° C., and then, FE-SEM of each module was used. The cross section was confirmed. FE-SEM images of each thermoelectric module are shown in FIGS. 6 to 8.
  • thermoelectric module of Example 2 even after the heat treatment at 400 ° C., a Ta deposition film was clearly present, and an alloy layer was not present in the sintered CoSb 3 , which is a thermoelectric semiconductor substrate. It was estimated that the Cu component was not diffused by the Ta deposition film into the thermoelectric semiconductor substrate.
  • thermoelectric module of Comparative Example 2 after the heat treatment at 400 ° C., the Ni component was diffused into the CoSb 3 sintered body to form an alloy layer (see “ ⁇ ” in FIG. 7).
  • the Sn component which is a solder component, was diffused into the CoSb 3 sintered body to form an alloy layer (see ' ⁇ ' part of FIG. 8).
  • thermoelectric device including the diffusion barrier layer according to the present invention had excellent thermal stability even at a high temperature of 400 ° C.
  • thermoelectric modules of Example 2 Comparative Examples 2 and 3 were measured for resistance to temperature changes, and the results are shown in FIG. 9.
  • thermoelectric module of Example 2 when the operating temperature of the thermoelectric module was gradually increased from 320 ° C. to 450 ° C., the resistance of the thermoelectric module of Example 2 increased from 3.3 kW to 3.8 kW, but the resistance change rate was small.
  • the temperature when the temperature was raised step by step from 320 °C to 450 °C, the resistance of the thermoelectric module of Comparative Example 2 increased from 3.5 kW to 5.7 kW, and the thermoelectric module of Comparative Example 3 became very large from 2.5 kW to 12.6 kW. . That is, in Comparative Examples 2 and 3, the resistance change rate was larger than that in Example 2.
  • thermoelectric device including the diffusion barrier layer according to the present invention has a small resistance change rate even when the use temperature is increased, and thus, the thermoelectric module may have a constant output value.
  • thermoelectric module using the thermoelectric device of the present invention has a low resistance even when used at a high temperature, it can be predicted that the output value of the thermoelectric module may be increased.

Abstract

The present invention relates to a thermoelectric element and a thermoelectric module including the same, wherein the thermoelectric element includes a diffusion preventing layer formed of at least one selected from the group consisting of tantalum (Ta), tungsten (W), molybdenum (Mo), and titanium (Ti).

Description

열전소자 및 이를 포함하는 열전모듈Thermoelectric element and thermoelectric module including same
본 발명은 열전소자 및 이를 포함하는 열전모듈에 관한 것이다.The present invention relates to a thermoelectric element and a thermoelectric module including the same.
일반적으로 열전소자(thermoelectric element)는 열과 전기의 상호 작용으로 나타나는 펠티어 효과(Peltier effect) 및 제베크 효과(Seebeck effect)를 이용한 각종 소자로서, 폐열발전 등의 열전발전이나 능동 냉각에 적용되고 있다. 이러한 열전소자는 솔더링(soldering) 또는 브레이징(Brazing)을 통해 전극에 접합된다. 이때, 전극은 주로 Cu 전극을 사용하는데, Cu 전극의 경우, 접합시 Cu 성분이나 솔더 성분이 열전소자 내부로 침투한다. 이로 인해, 열전소자의 열전 성능이 낮아지거나, 또는 침투한 Cu가 열전소자의 성분과 금속간 화합물을 형성하여 기계적 특성을 저하시키는 문제가 발생하였다.In general, thermoelectric elements are various devices using the Peltier effect and the Seebeck effect, which are caused by the interaction between heat and electricity, and are applied to thermoelectric generation and active cooling such as waste thermal power generation. The thermoelectric element is bonded to the electrode through soldering or brazing. At this time, the electrode mainly uses a Cu electrode, in the case of the Cu electrode, the Cu component or the solder component penetrates into the thermoelectric element during bonding. As a result, the thermoelectric performance of the thermoelectric element is lowered or the penetrated Cu forms an intermetallic compound with the components of the thermoelectric element, thereby causing a problem of deteriorating mechanical properties.
이에, Cu 등의 확산을 방지하기 위해서, 종래에는 표면에 Ni 도금층이 형성된 열전소자를 개발하였다. 그러나, 종래 열전소자에서, Ni 도금층은 두께가 약 0.3 내지 3 ㎛ 정도로 얇을 경우, 확산방지의 역할을 충실히 수행하기 어렵다. 이를 해결하기 위해 종래 열전소자는 Ni 도금층을 약 20 내지 40 ㎛ 수준으로 두껍게 형성하였고, 이로 인해 저항이 증가하여 열전모듈의 출력값이 저하되었다. 또한, 종래 열전소자의 경우, 고온에서의 접합 안정성이 여전히 저하되었고, 400 ℃ 이상의 고온에서 열적 안정성이 저하되어, Ni 자체가 열전소자 내부로 확산되는 문제가 발생하였다. Accordingly, in order to prevent diffusion of Cu or the like, a thermoelectric device in which a Ni plating layer is formed on a surface thereof has been developed. However, in the conventional thermoelectric element, when the Ni plating layer is as thin as about 0.3 to 3 μm, it is difficult to faithfully perform the role of diffusion prevention. In order to solve this problem, the conventional thermoelectric device has a thick Ni plating layer formed at a level of about 20 to 40 μm, thereby increasing resistance and lowering the output value of the thermoelectric module. In addition, in the case of the conventional thermoelectric device, the bonding stability at a high temperature is still lowered, and the thermal stability at a high temperature of 400 ° C. or more is lowered, causing a problem that Ni itself diffuses into the thermoelectric device.
따라서, 고온에서의 열적 안정성, 접합 안정성 및 두께에 따른 열전 성능이 우수한 열전소자의 개발이 필요하다.  Therefore, it is necessary to develop a thermoelectric device having excellent thermoelectric performance according to thermal stability, junction stability, and thickness at high temperature.
본 발명은 고온에서의 열적 안정성 및 접합 안정성이 우수하고, 열전 성능이 우수한 열전소자를 제공하는 것을 목적으로 한다.An object of the present invention is to provide a thermoelectric element which is excellent in thermal stability and bonding stability at high temperature and excellent in thermoelectric performance.
또, 본 발명은 상기 열적소자를 포함하여 고온의 사용 온도대를 갖는 열전모듈을 제공하는 것을 다른 목적으로 한다.In addition, another object of the present invention is to provide a thermoelectric module having a high temperature use temperature band including the thermal element.
상기 목적을 달성하기 위해서, 본 발명은 벌크형 열전반도체 기재; 및 상기 벌크형 열반도체 기재의 표면에, 탄탈늄(Ta), 텅스텐(W), 몰리브덴(Mo) 및 티타늄(Ti)으로 이루어진 군에서 선택된 적어도 하나로 형성된 확산방지층을 포함하는 열전소자를 제공한다.In order to achieve the above object, the present invention is a bulk type thermoelectric semiconductor substrate; And a diffusion barrier layer formed on at least one selected from the group consisting of tantalum (Ta), tungsten (W), molybdenum (Mo), and titanium (Ti) on the surface of the bulk thermal semiconductor substrate.
여기서, 상기 벌크형 열전반도체 기재는 표면조도(Ra)가 0.5 내지 3.0 ㎛ 범위인 것이 바람직하다.Here, the bulk type thermoelectric substrate preferably has a surface roughness (Ra) of 0.5 to 3.0 ㎛ range.
또, 상기 확산방지층은 두께가 0.3 내지 20 ㎛ 범위인 것이 바람직하다.In addition, the diffusion barrier layer is preferably in the range of 0.3 to 20 ㎛ thickness.
또, 상기 확산방지층 위에 니켈(Ni)층을 형성할 수 있다.In addition, a nickel (Ni) layer may be formed on the diffusion barrier layer.
이러한 열전소자는 열전발전용인 것이 바람직하다.It is preferable that such a thermoelectric element is dedicated to thermo development.
또한, 본 발명은 전술한 열전소자를 포함하는 열전모듈을 제공한다.In addition, the present invention provides a thermoelectric module including the above-mentioned thermoelectric element.
본 발명의 열전소자는 탄탈늄(Ta), 텅스텐(W), 몰리브덴(Mo) 및 티타늄(Ti)으로 이루어진 군에서 선택된 적어도 하나로 형성된 확산방지층을 포함함으로써, 종래 열전소자와 유사한 열전 성능을 가지면서, 종래 열전소자에 비해 고온에서의 열적 안정성 및 접합 안정성이 우수하다. 따라서, 본 발명의 열전소자를 포함하는 열전모듈은 종래 열전모듈보다 높은 온도 대에서 사용될 수 있고, 나아가 발전 출력을 향상시킬 수 있다.The 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), thereby having a thermoelectric performance similar to that of a conventional thermoelectric device. In comparison with the conventional thermoelectric device, thermal stability and bonding stability at high temperature are excellent. Therefore, the thermoelectric module including the thermoelectric device of the present invention can be used at a higher temperature range than the conventional thermoelectric module, and further improve the power generation output.
도 1은 본 발명의 일례에 따른 열전소자를 나타낸 단면도이다.1 is a cross-sectional view showing a thermoelectric device according to an example of the present invention.
도 2는 본 발명의 다른 일례에 따른 열전소자를 나타낸 단면도이다.2 is a cross-sectional view illustrating a thermoelectric device according to another exemplary embodiment of the present invention.
도 3은 본 발명의 일례에 따른 열전모듈을 나타낸 사시도이다.3 is a perspective view showing a thermoelectric module according to an example of the present invention.
도 4는 열처리한 실시예 1의 열전모듈의 단면을 나타낸 전계방사 주사전자현미경(Field Emission Scanning electron microscope, FE-SEM) 사진이다. 4 is a field emission scanning electron microscope (FE-SEM) photograph showing a cross section of the thermoelectric module of Example 1 after heat treatment.
도 5는 비교예 1에서 제조된 열전모듈의 단면을 나타낸 FE-SEM 사진으로, (a)는 열처리 하기 전의 FE-SEM 사진이고, (b)는 열처리한 후의 FE-SEM 사진이다.5 is a FE-SEM picture showing a cross section of the thermoelectric module manufactured in Comparative Example 1, (a) is a FE-SEM picture before the heat treatment, (b) is a FE-SEM picture after the heat treatment.
도 6은 열처리한 실시예 2의 열전모듈의 단면을 나타낸 FE-SEM 사진이다.6 is a FE-SEM photograph showing a cross section of the thermoelectric module of Example 2 after heat treatment.
도 7은 열처리한 비교예 2의 열전모듈의 단면을 나타낸 FE-SEM 사진이다.7 is a FE-SEM photograph showing a cross section of the thermoelectric module of Comparative Example 2 subjected to heat treatment.
도 8은 열처리한 비교예 3의 열전모듈의 단면을 나타낸 FE-SEM 사진이다.8 is a FE-SEM photograph showing a cross section of the thermoelectric module of Comparative Example 3 subjected to heat treatment.
도 9는 온도 변화에 따른 실시예 2, 비교예 2 및 3의 열전모듈의 저항 변화를 나타낸 그래프이다.9 is a graph showing the resistance change of the thermoelectric module of Example 2, Comparative Examples 2 and 3 according to the temperature change.
* 부호의 설명** Explanation of Codes *
10: 열전소자, 11: 벌크형 열전반도체 기재, 10: thermoelectric element, 11: bulk type thermoelectric semiconductor substrate,
12: 확산방지층, 13: 니켈층,12: diffusion barrier layer, 13: nickel layer,
10a: p형 열전소자, 10b: n형 열전소자,10a: p-type thermoelectric element, 10b: n-type thermoelectric element,
21: 상부 전극, 22: 하부 전극, 21: upper electrode, 22: lower electrode,
31: 상부 기판, 32: 하부 기판,31: upper substrate, 32: lower substrate,
100: 열전모듈100: thermoelectric module
이하, 본 발명을 설명한다.Hereinafter, the present invention will be described.
본 발명자들은 탄탈늄(Ta), 텅스텐(W), 몰리브덴(Mo) 및 티타늄(Ti) 등과 같은 금속을 열전반도체 기재의 표면에 형성할 경우, 열전소자와 전극과의 고온 접합시 벌크형 열전반도체 기재와 전극 간의 확산 방지 효과 및 고온에서의 접합 안정성이 우수하다는 것을 알았다.The present inventors found that when 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 thermoconductor substrate during high temperature bonding of a thermoelectric element and an electrode It was found that the effect of preventing diffusion between the electrode and the electrode and the bonding stability at high temperature were excellent.
본 발명에서 탄탈늄(Ta), 텅스텐(W), 몰리브덴(Mo) 및 티타늄(Ti)은 약 1600 ℃ 이상의 높은 용융점을 갖는 금속으로, 전극 성분(예컨대, Cu, Au, Ag 등)보다 용융점이 높기 때문에, 약 300 ℃ 이상의 고온에서도 열역학적으로 안정적이고, 전극과 화학적으로 반응하지 않거나 반응하더라도 반응 속도가 느리다. 따라서, 상기 열전소자가 상기 금속으로 형성된 확산방지층을 포함함으로써, 상기 열전소자가 솔더링(soldering) 또는 브레이징(brazing)을 통해 전극 등에 접합될 때, 상기 확산방지층은 두께가 약 0.3 ~ 5 ㎛로 얇더라도, 전극 성분이나 솔더 성분 등이 벌크형 열전반도체 기재 내로 확산되는 것을 방지할 수 있다. 뿐만 아니라, 상기 열전소자를 포함하는 열전모듈이 약 300 ℃ 이상의 온도에서 사용되더라도, 상기 확산방지층이 열역학적으로 안정하기 때문에, 상기 확산방지층은 별도의 층간 접착층 없이도 열전반도체 기재와 전극 간의 접합 상태를 안정적으로 유지할 수 있다. 게다가, 상기 금속은 전기전도도 및 열전도도가 우수하고, 전극(예컨대, Cu 등)이나 기판에 대한 접촉저항(contact resistivity)이 작기 때문에, 상기 확산방지층은 열전반도체 기재에서 발생하는 열이나 전기의 이동을 방해하지 않고, 따라서 열전소자의 열전 성능 저하를 초래하지 않는다. 아울러, 상기 확산방지층의 성분 중 탄탈늄(Ta) 및 티타늄(Ti)은 열팽창계수가 열전반도체 기재 및/또는 전극과 유사하다. 따라서, 상기 확산방지층이 Ta 및/또는 Ti로 형성된 열전소자의 경우, 상기 확산방지층과 열전반도체 기재 및/또는 전극 사이의 열팽창계수(Coefficient of Thermal Expansion, CTE) 차이가 작기 때문에, 사용시 열피로도가 작고, 따라서 수명 특성이 향상될 수 있다.In the present invention, tantalum (Ta), tungsten (W), molybdenum (Mo) and titanium (Ti) are metals having a high melting point of about 1600 ° C. or higher, and have a melting point higher than that of electrode components (eg, Cu, Au, Ag, etc.). Because of its high temperature, 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 chemically react 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 or the like through soldering or brazing, the diffusion barrier layer is thin with a thickness of about 0.3 to 5 μm. Even if the electrode component, the solder component, or the like can be prevented from being diffused into the bulk type thermoelectric substrate. In addition, even when the thermoelectric module including the thermoelectric element is used at a temperature of about 300 ° C. or more, since the diffusion barrier layer is thermodynamically stable, the diffusion barrier layer is stable in the bonding state between the thermoelectric semiconductor substrate and the electrode without a separate interlayer adhesive layer. Can be maintained. In addition, since the metal has excellent electrical conductivity and thermal conductivity, and has low contact resistivity with respect to an electrode (for example, Cu, etc.) or a substrate, the diffusion barrier layer is used to transfer heat or electricity generated from the thermoelectric substrate. Does not disturb, and thus does not cause a decrease in thermoelectric performance of the thermoelectric element. In addition, tantalum (Ta) and titanium (Ti) among the components of the diffusion barrier layer have a coefficient of thermal expansion similar to that of a thermoelectric semiconductor substrate and / or an electrode. Therefore, in the case of a thermoelectric device in which the diffusion barrier layer is formed of Ta and / or Ti, the thermal fatigue rate of the diffusion barrier layer and the thermoelectric semiconductor substrate and / or the electrode is small, so that the thermal fatigue rate in use is small. Small, and thus lifespan characteristics can be improved.
이에, 본 발명에 따른 열전소자는 Ta, W, Mo 및 Ti으로 이루어진 군에서 선택된 적어도 하나로 형성된 확산방지층을 벌크형 열전반도체 기재의 표면에 배치하는 것을 특징으로 한다. 이로써, 본 발명의 열전소자는 종래 열전소자와 유사한 열전 성능을 가지면서, 종래 열전소자에 비해 고온에서의 열적 안정성 및 접합 안정성이 우수하고, 나아가 열전모듈의 사용 온도대를 높일 수 있어, 열전모듈의 발전 출력을 향상시킬 수 있다.Thus, the thermoelectric device according to the present invention 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. As a result, the thermoelectric device of the present invention has a thermoelectric performance similar to that of the conventional thermoelectric device, and is superior in thermal stability and bonding stability at high temperature as compared with the conventional thermoelectric device, and further increases the use temperature range of the thermoelectric module. Can improve the power output.
<열전소자><Thermoelectric element>
본 발명의 열전소자(10)는 도 1에 도시된 바와 같이, 벌크형 열전반도체 기재(11) 및 확산방지층(12)을 포함한다. 선택적으로, 본 발명의 열전소자(10)는 니켈(Ni)층(13)을 더 포함할 수 있다(도 2 참조).As shown in FIG. 1, the thermoelectric element 10 of the present invention includes a bulk type thermoelectric semiconductor substrate 11 and a diffusion barrier layer 12. Optionally, the thermoelectric element 10 of the present invention may further include a nickel (Ni) layer 13 (see FIG. 2).
본 발명에서 사용 가능한 열전반도체 기재는 전기가 인가되면 양단에 온도차가 발생하거나, 또는 그 양단에 온도 차이가 발생하면 전기가 발생하는 재료로 형성되는데, 양단의 온도차에 의해 전기가 발생하는 재료인 것이 바람직하다. 예를 들어, 비스무트(Bi), 텔루륨(Te), 셀레늄(Se), 안티몬(Sb), 구리(Cu), 요오드(I)로 이루어진 군에서 선택된 적어도 하나로 형성될 수 있는데, 이에 한정되지 않는다. 일례에 따르면, 상기 열전반도체 기재는 Bi-Te-Se계 열전반도체 기재일 수 있다. 다른 일례에 따르면, Skutterudite계 열전반도체 기재일 수 있다.The thermoconductor substrate usable in the present invention is formed of a material that generates electricity when a temperature difference occurs 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. desirable. 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. . According to one example, the thermoconductor substrate may be a Bi-Te-Se-based thermoconductor substrate. According to another example, it may be a Skutterudite-based thermoelectric semiconductor substrate.
또한, 본 발명에서는 분말 소결법 등에 의해 형성되어 부피가 큰 벌크형 열전반도체 기재를 사용한다. 상기 벌크형 열전반도체 기재는 박막형 열전반도체 기재와 달리 두께가 두껍기 때문에, 두께 방향으로의 온도 차이가 크다. 따라서, 벌크형 열전반도체 기재를 포함하는 본 발명의 열전소자는 제베크 효과를 이용한 열전발전시스템에 용이하게 적용될 수 있다.In the present invention, a bulky thermoconductor substrate formed by a powder sintering method or the like is used. Since the bulk type thermoelectric substrate is thicker than the thin film type thermoelectric substrate, the temperature difference in the thickness direction is large. Therefore, the thermoelectric element 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.
이러한 벌크형 열전반도체 기재는 p형 벌크 열전반도체 기재 또는 n형 벌크 열전반도체 기재일 수 있으며, 이에 따라 본 발명의 열전소자가 p형 열전소자 또는 n형 열전소자일 수 있다.The bulk thermoelectric substrate may be a p-type bulk thermoelectric substrate or an n-type bulk thermoelectric substrate, and thus the thermoelectric device of the present invention may be a p-type thermoelectric device or an n-type thermoelectric device.
상기 벌크형 열전반도체 기재의 표면조도(Ra)는 특별히 한정되지 않으나, 약 0.5 내지 3.0 ㎛ 범위일 경우, 결함(defect)없이 확산방지층과의 접착성이 향상될 수 있다.The surface roughness Ra of the bulk thermoelectric substrate is not particularly limited, but in the range of about 0.5 to 3.0 μm, adhesion to the diffusion barrier layer may be improved without a defect.
또, 상기 벌크형 열전반도체 기재의 두께는 특별히 한정되지 않는다. 다만, 상기 벌크형 열전반도체 기재의 두께가 너무 얇아 방열부(hot side)와 냉각부(cold side) 사이의 거리가 너무 가까우면, 간섭에 의해 온도 편차가 발생하는 구간이 너무 작을 수 있다. 한편, 상기 벌크형 열전반도체 기재의 두께가 너무 두꺼워서 방열부와 냉각부 사이의 거리가 너무 멀면, 높은 열전 성능 지수(ZT)을 갖는 온도 분포를 나타내는 열전소자 영역이 상대적으로 적어 효율이 낮아질 수 있다. 따라서, 상기 벌크형 열전반도체 기재의 두께는 약 1 내지 5 ㎜ 범위인 것이 바람직하다. In addition, the thickness of the said bulk type thermoconductor base material is not specifically limited. However, if the thickness of the bulk type thermoelectric semiconductor substrate is too thin and the distance between the hot side and the cold side is too close, a section in which the temperature deviation occurs due to interference may be too small. On the other hand, if the thickness of the bulk type thermoelectric semiconductor substrate is too thick and the distance between the heat dissipation portion and the cooling portion is too long, the thermoelectric element region exhibiting 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 thermoconductor substrate is preferably in the range of about 1 to 5 mm.
이와 같은 벌크형 열전반도체 기재는 당 기술분야에서 알려진 열전재료의 제조방법에 따라 형성될 수 있다. 예를 들어, 상기 열전반도체 기재는 원재료 분말을 용해시키고, 용융방사 회전법(melt-spinning)이나 기상원자화법(gas atomization) 등을 수행한 후 가압소결법을 순차적으로 진행하여 제조될 수 있다.Such a bulk thermoelectric semiconductor substrate may be formed according to a method for manufacturing a thermoelectric material known in the art. For example, the thermoelectric semiconductor substrate may be prepared by dissolving raw material powder, performing melt-spinning or gas atomization, and then sequentially performing pressure sintering.
상기 확산방지층(12)은 상기 열전반도체 기재(11)의 표면에 탄탈늄(Ta), 텅스텐(W), 몰리브덴(Mo), 티타늄(Ti) 및 이들의 합금으로 이루어진 군에서 선택된 물질로 형성된다. 이때, 열전반도체 기재 및 전극의 종류에 따라 적절한 금속을 사용하며, 열피로도 및 수명 특성 측면에서, 열전반도체 기재 및/또는 전극과의 열팽창계수 차이가 작은 Ta 및/또는 Ti를 확산방지층의 성분으로 사용하는 것이 바람직하다. 이러한 확산방지층(12)은 전술한 바와 같이, 열전반도체 기재와 전극 간의 상호 확산을 지연 또는 방지하면서, 전극에 대한 열전소자의 접합성(접착성)을 향상시킬 수 있다. 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. . In this case, an appropriate metal is used according to the type of the thermoconductor substrate and the electrode, and in terms of thermal fatigue and life characteristics, Ta and / or Ti having a small difference in coefficient of thermal expansion between the thermoconductor substrate and / or the electrode are used as components of the diffusion barrier layer. It is preferable to use. As described above, the diffusion barrier layer 12 may improve the adhesion (adhesiveness) of the thermoelectric element to the electrode while delaying or preventing mutual diffusion between the thermoelectric semiconductor substrate and the electrode.
상기 확산방지층의 두께는 특별히 한정되지 않으나, 열전반도체 기재의 종류에 따른 열전성능지수(ZT)을 고려하여 조절하는 것이 바람직하다. 일례에 따르면, 상기 열전반도체 기재가 Bi-Te-Se계 열전반도체 기재인 경우, 상기 확산방지층의 두께를 약 0.3 내지 20 ㎛ 범위, 바람직하게 약 0.5 내지 3 ㎛ 범위로 조절하면, 확산방지층의 저항이 감소하기 때문에, 열전모듈의 출력값이 향상될 수 있어 바람직하다.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. According to one example, when the thermoconductor substrate is a Bi-Te-Se based thermoconductor substrate, if the thickness of the diffusion barrier layer is adjusted to about 0.3 to 20 ㎛ range, preferably about 0.5 to 3 ㎛ range, the resistance of the diffusion barrier layer Since this decreases, the output value of the thermoelectric module can be improved, which is preferable.
이와 같은 확산방지층은 당 기술분야에서 알려진 박막 형성 방법에 따라 형성될 수 있다. 예를 들어, 스퍼터링 증착, 열증발 진공 증착 등과 같은 물리적 기상 증착법; 상압 화학적 증착, 저압 화학적 증착, 플라즈마 화학적 증착 등과 같은 화학적 기상 증착법; 도금법 등이 있는데, 이에 한정되지 않는다. 다만, 상기 확산방지층은 스퍼터링 증착법에 의해 박막 형태로 벌크형 열전반도체 기재 상에 형성되는 것이 바람직하다. 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 methods such as atmospheric chemical vapor deposition, low pressure chemical vapor deposition, plasma chemical vapor deposition, and the like; There is a plating method, but the present invention is not limited thereto. However, the diffusion barrier layer is preferably formed on the bulk type thermoelectric substrate in the form of a thin film by sputter deposition.
상기 스퍼터링 증착 조건은 특별히 한정되지 않으나, 기판으로 Si Plate 등을 사용할 수 있으며, 공정 가스로 아르곤(Ar) 등을 사용하고, 진공도는 약 0.5 내지 2 Pa 범위이며, 인가 전압은 약 800 내지 1200 W 범위이고, 온도는 상온, 바람직하게 약 19 내지 22 ℃ 범위이며, 증착 속도는 약 7 내지 15 Å/sec 범위일 수 있다.The sputtering deposition conditions are not particularly limited, but a Si plate or the like may be used as a substrate, and argon (Ar) may be used as a process gas, and a vacuum degree is in a range of about 0.5 to 2 Pa, and an applied voltage is about 800 to 1200 W. Range, the temperature is at room temperature, preferably in the range of about 19-22 ° C., and the deposition rate may be in the range of about 7-15 μs / sec.
선택적으로, 본 발명에 따른 열전소자는 도 2에 도시된 바와 같이, 전술한 확산방지층(12) 상에 니켈(Ni)층(13)을 더 형성할 수 있다. 상기 니켈층(13)은 확산방지층의 접합력을 보조하는 층으로, 열전모듈의 제조시 솔더와 열전소자 간의 접합력을 향상시킬 수 있다.Optionally, in the thermoelectric device according to the present invention, as shown in FIG. 2, the nickel (Ni) layer 13 may be further formed on the diffusion barrier layer 12 described above. The nickel layer 13 is a layer that assists the bonding force of the diffusion barrier layer, and may improve the bonding force between the solder and the thermoelectric element when the thermoelectric module is manufactured.
이러한 니켈층의 두께는 특별히 한정되지 않는다. 다만, 본 발명의 경우, 확산방지층(12)이 전극 성분 등의 확산을 방지하고 있기 때문에, 니켈층의 두께는 종래 열전소자의 니켈 층의 두께와 동일하거나 또는 얇아도 상관없다. 예컨대, 상기 니켈 층의 두께는 약 1 내지 20 ㎛ 범위일 수 있다. The thickness of such a nickel layer is not specifically limited. However, in the case of the present invention, since the diffusion barrier layer 12 prevents diffusion of electrode components and the like, the thickness of the nickel layer may be the same as or thinner than that of the nickel layer of the conventional thermoelectric element. For example, the thickness of the nickel layer may range from about 1 to 20 μm.
상기 니켈층(13)은 당해 기술분야에서 알려진 형성 방법, 예컨대 도금법 등에 의해 형성될 수 있고, 특별히 한정되지 않는다.The nickel layer 13 may be formed by a formation method known in the art, for example, a plating method and the like, and is not particularly limited.
전술한 열전소자의 형상은 특별히 한정되지 않으며, 예컨대 직육면체 형상 등일 수 있다.The shape of the above-mentioned thermoelectric element is not particularly limited, and may be, for example, a rectangular parallelepiped shape.
<열전모듈><Thermoelectric Module>
또, 본 발명은 열전냉각시스템 또는 열전발전시스템에 이용될 수 있는 열전모듈을 제공하는데, 상기 열전모듈은 전술한 열전소자를 포함함으로써, 고온의 사용 온도대를 갖기 때문에 발전 출력이 높일 수 있다.In addition, the present invention provides a thermoelectric module that can be used in a thermoelectric cooling system or a thermoelectric power generation system. The thermoelectric module includes the above-mentioned thermoelectric element, and thus the power generation output can be increased because it has a high temperature use temperature band.
일례로, 상기 열전모듈(100)은 도 3에 도시된 바와 같이, p형 열전소자(10a), n형 열전소자(10b), 상부 전극(21), 하부 전극(22), 상부 기판(31) 및 하부 기판(32)을 포함하되, 상기 p형 열전소자(10a) 및 n형 열전소자(10b) 중 적어도 어느 하나는 전술한 열전소자(10)이다(도 1~2 참조). For example, as illustrated in FIG. 3, the thermoelectric module 100 includes 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 FIGS. 1 and 2).
상기 열전모듈(100)에서, 상기 p형 열전소자(10a) 및 n형 열전소자(10b)는 각각 1개 또는 복수개이며, 이들은 일방향으로 교번하여 배치되어 매트릭스 형상을 형성한다. 이때, 각 열전소자(10a, 10b)의 확산방지층(12)은 상부 전극(21) 및 하부 전극(22)과의 접합부에 위치하여, 열전반도체 기재(11)와 전극(21, 22) 사이의 확산을 방지하면서, 고온에서 안정적으로 전극(21, 22)과의 접합을 유지할 수 있다. 따라서, 본 발명의 열전모듈(100)은 약 300 ℃ 이상의 고온에서 사용될 수 있을 뿐만 아니라, 발전 출력이 향상될 수 있다.In the thermoelectric module 100, the p-type thermoelectric element 10a and the n-type thermoelectric element 10b are each one or plural, and they are alternately arranged in one direction to form a matrix shape. At this time, the diffusion barrier layer 12 of each thermoelectric element (10a, 10b) is located in the junction between 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. Therefore, the thermoelectric module 100 of the present invention can be used at a high temperature of about 300 ° C. or more, and the power generation output can be improved.
상기 상부 전극(21) 및 하부 전극(22)은 일방향으로 이웃하는 상기 p형 열전소자와 n형 열전소자의 상면 및 하면을 각각 전기적으로 연결한다. 이러한 상부 및 하부 전극(21, 22)은 각각 알루미늄, 니켈, 금, 구리, 은 등과 같은 물질로 형성될 수 있는데, 이에 한정되지 않는다.The upper electrode 21 and the lower electrode 22 electrically connect the upper and lower surfaces of the p-type thermoelectric element and the n-type thermoelectric element which are adjacent in one direction, respectively. The upper and lower electrodes 21 and 22 may be formed of a material such as aluminum, nickel, gold, copper, silver, and the like, but is not limited thereto.
상기 상부 기판(31)은 상기 상부 전극(21)의 외측 표면에 배치되어 발열(또는 흡열)하고, 상기 하부 기판(32)은 상기 하부 전극(22)의 외측 표면에 배치되어 흡열(또는 발열)하는 전기 절연 소재이다. 이러한 기판(31, 32)의 비제한적인 예로는 사파이어, 실리콘, 석영 기판 등이 있다.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). Is an electrical insulation material. Non-limiting examples of such substrates 31 and 32 include sapphire, silicon, quartz substrates, and the like.
선택적으로, 상기 열전모듈은 상기 열전소자(11, 12)와 전극(21, 22) 사이에 솔더층(미도시됨)을 더 포함할 수 있고, 또는 상기 열전소자 사이에 형성된 절연필름(미도시됨)을 더 포함할 수 있다.Optionally, the thermoelectric module 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).
이와 같은 열전모듈은 당 기술분야에서 알려진 통상의 방법에 따라 제조될 수 있다.Such thermoelectric modules may be manufactured according to conventional methods known in the art.
이하, 본 발명을 실시예를 통해 구체적으로 설명하나, 하기 실시예 및 실험예는 본 발명의 한 형태를 예시한 것에 불과할 뿐이며, 본 발명의 범위가 하기 실시예 및 실험예에 의해 제한되는 것은 아니다.Hereinafter, the present invention will be described in detail by way of 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 to the following Examples and Experimental Examples. .
[[ 실시예Example 1]  One]
1-1. p형 및 n형 열전소자의 제조1-1. Fabrication of p-type and n-type Thermoelectric Devices
5N 이상의 고순도를 갖는 Bi, Te, Sb 및 Se 원재료를 준비하였다. 이때, p형 열전재료의 경우, Bi, Te 및 Sb 원재료가 Bi0 . 44Te3Sb1 .56의 목표 조성을 갖도록 각각 칭량하였고, n형 열전재료의 경우, Bi, Te 및 Se 원재료가 Bi2Te2 . 7Se0 .3의 목표 조성을 갖도록 각각 칭량하였으며, Te의 휘발을 고려하여 1 wt%의 Te를 더 추가하였다. 이후, 각 재료를 석영관(Quartz ampoule)에 장입한 후, 약 10-2 Torr의 진공도에서 석영관을 진공 상태로 밀봉하고, 진공 밀봉된 석영관을 Knocking Furnace에 장입한 후, 약 1033 K에서 10회/min의 속도로 2시간 동안 교반 및 용해시킨 다음, 공냉시켜 모합금 잉곳을 제조하였다. 이후, 모합금 잉곳을, 용융 방사 장비를 이용하여 약 1000 rpm의 구리 휠 회전속도 및 약 0.5 MPa의 분사 압력으로 분사시켜, 금속 리본을 제조하였다. 이후, 형성된 금속 리본을, 방전플라즈마 소결(spark plasma sintering, SPS)을 이용하여 약 480 ℃에서 약 3 분 동안 약 40 MPa의 소결압력으로 가압 소결하여 소결체(직경: Φ50, 두께: 15 ㎜)를 제조하였다. 이후, 상기 소결체를 슬라이싱(slicing)(두께: 5 mm)한 다음, 소결체의 표면조도(Ra)를 약 1.4 ㎛로 조절하였다. 이어서, Ta Sputter를 이용하여 1,000 W의 인가 전압 및 7.85 Å/sec의 증착속도로 상기 소결체의 표면에 Ta 막(두께: 0.5 ㎛)을 증착한 다음, 다이싱(Dicing)하여 펠렛 형태의 열전소자를 제조하였다.Bi, Te, Sb and Se raw materials having high purity of 5N or more were prepared. At this time, in the case of the p-type thermoelectric material, Bi, Te and Sb raw materials are Bi 0 . Te 44 Sb 3 were each weighed so as to have the composition of the target 1 .56, in the case of the n-type thermoelectric materials, Bi, Te and Se raw material is Bi 2 Te 2. 7 Se 0 .3 target composition were each weighed so as to have a, Te was added to the 1 wt% more in consideration of the evaporation of Te. Thereafter, each material was charged into a quartz tube (Quartz ampoule), the quartz tube was sealed in a vacuum state at a vacuum degree of about 10 -2 Torr, and the vacuum-sealed quartz tube was charged into a Knocking Furnace, and then at about 1033 K. A master alloy ingot was prepared by stirring and dissolving at a rate of 10 times / min for 2 hours and then air cooling. The master alloy ingot was then sprayed using melt spinning equipment at a copper wheel rotation speed of about 1000 rpm and an injection pressure of about 0.5 MPa to produce a metal ribbon. Thereafter, the formed metal ribbon was pressed and sintered at a sintering pressure of about 40 MPa at about 480 ° C. for about 3 minutes using spark plasma sintering (SPS) to obtain a sintered body (diameter: Φ50, thickness: 15 mm). Prepared. Thereafter, the sintered body was sliced (thickness: 5 mm), and then the surface roughness Ra of the sintered body was adjusted to about 1.4 μm. Subsequently, a Ta film (thickness: 0.5 μm) was deposited on the surface of the sintered body at an applied voltage of 1,000 W and a deposition rate of 7.85 Å / sec using Ta Sputter, followed by dicing to pellet-type thermoelectric element. Was prepared.
1-2. 열전모듈의 제조1-2. Manufacture of Thermoelectric Module
제1 Cu 전극과 제2 Cu 전극 사이에, 실시예 1-1에서 각각 제조된 p형 열전소자 및 n형 열전소자를 약 300 ℃에서 납땜을 통해 접합하여 열전모듈을 제조하였다.A p-type thermoelectric element and an n-type thermoelectric element respectively manufactured in Example 1-1 were bonded between the first Cu electrode and the second Cu electrode by soldering at about 300 ° C. to prepare a thermoelectric module.
[비교예 1]Comparative Example 1
실시예 1-1에서 소결체의 표면에 Ta 증착막을 형성하는 대신 약 30 ㎛의 Ni 도금막을 형성하는 것을 제외하고는, 실시예 1과 동일하게 수행하여 p형 및 n형 열전소자와, 열전모듈을 제조하였다.A p-type and n-type thermoelectric element and a thermoelectric module were formed in the same manner as in Example 1 except that a Ni plating film having a thickness of about 30 μm was formed instead of forming a Ta deposition film on the surface of the sintered body in Example 1-1. Prepared.
[실험예 1] - 고온 안정성 측정 1Experimental Example 1-High Temperature Stability Measurement 1
실시예 1 및 비교예 1에서 각각 제조된 열전모듈의 고온 안정성을 확인하기 위해서, 각 열전모듈을 300 ℃에서 열처리한 다음, 열전모듈의 단면을 전계방사 주사현미경을 이용하여 나타내었다. FE-SEM 사진은 각각 도 4 및 5에 나타내었다.In order to confirm the high temperature stability of the thermoelectric modules manufactured in Example 1 and Comparative Example 1, each thermoelectric module was heat-treated at 300 ℃, and then the cross-section of the thermoelectric module was shown by using an electric field scanning scanning microscope. FE-SEM images are shown in FIGS. 4 and 5, respectively.
실시예 1의 열전모듈은 300 ℃의 열처리 후에도 열전반도체 기재인 소결체 표면 위에 Ta 증착막이 존재하고 있었다.In the thermoelectric module of Example 1, a Ta deposited film was present on the surface of the sintered body which is a thermoelectric semiconductor substrate even after the heat treatment at 300 ° C.
반면, 비교예 1의 열전모듈은 열처리하기 전에 Cu 전극과 소결체 사이의 경계면에 Ni 도금막이 존재하였으나, 열처리 후 Cu 전극과 소결체 사이의 경계에 Ni 도금막이 거의 보이지 않았고, Cu 전극의 분포가 넓어진 것을 확인할 수 있었다. 이는 Ni 도금막의 Ni가 약 300 ℃ 이상의 고온에서 소결체 내로 확산되어 손실된 것으로 추정되었다.On the other hand, in the thermoelectric module of Comparative Example 1, the Ni plated film existed at the interface between the Cu electrode and the sintered body before the heat treatment, but the Ni plated film was hardly visible at the boundary between the Cu electrode and the sintered body, and the distribution of the Cu electrode was widened. I could confirm it. It was estimated that Ni in the Ni plated film was diffused into the sintered body at a high temperature of about 300 ° C. or more and lost.
이와 같이, 본 발명에 따른 확산방지층을 포함하는 열전소자를 이용한 열전모듈은 고온 안정성이 우수하다는 것을 확인할 수 있었다.As such, it was confirmed that the thermoelectric module using the thermoelectric device including the diffusion barrier layer according to the present invention has excellent high temperature stability.
[실시예 2]Example 2
2-1. 고온용 열전 소자의 제조2-1. Fabrication of high temperature thermoelectric elements
Skutterudite계 열전 소재인 CoSb3 소결체를 슬라이싱(slicing)(두께: 5 mm)한 다음, 소결체의 표면조도를 약 1.5 ㎛으로 조절하였다. 이후, Sputter를 이용하여 1,000 W의 인가 전압 및 7.85 Å/sec의 증착속도로 상기 CoSb3 소결체의 양 표면 상에, Ta 막(두께: 0.5 ㎛)을 증착한 다음, Ni 도금을 진행하여 Ni 도금층(두께: 5 ㎛)을 형성하였다. 이후, 다이싱(Dicing)하여 Pellet 형태의 열전 소자를 제조하였다. After slicing (thickness: 5 mm) the CoSb 3 sintered body, which is a skutterudite-based thermoelectric material, the surface roughness of the sintered body was adjusted to about 1.5 μm. Subsequently, a Ta film (thickness: 0.5 μm) was deposited on both surfaces of the CoSb 3 sintered body at an applied voltage of 1,000 W and a deposition rate of 7.85 μs / sec using a sputter, and then Ni plating was performed to carry out Ni plating. (Thickness: 5 mu m) was formed. Then, dicing (Dicing) to produce a thermoelectric device of the pellet type.
2-2. 열전 모듈의 제조 2-2. Manufacturing of thermoelectric modules
제1 DBC(Direct Bonded Copper) 기판의 구리측 표면과 실시예 2-1에서 제조된 열전 소자의 일면을 브레이징(brazing)한 다음, 상기 열전소자의 타면과 제 2 DBC 기판의 구리측 표면을 솔더링하여 열전 모듈을 제조하였다. After brazing the copper side surface of the first DBC substrate and one surface of the thermoelectric element manufactured in Example 2-1, soldering the other side of the thermoelectric element and the copper side surface of the second DBC substrate To prepare a thermoelectric module.
[비교예 2]Comparative Example 2
실시예 2-1에서 CoSb3 소결체의 표면에 Ta 증착막을 형성하지 않고, Ni 도금층을 두께 약 5 ㎛으로 형성하는 것을 제외하고는, 실시예 2와 동일하게 수행하여 열전소자 및 열전모듈을 제조하였다.A thermoelectric device and a thermoelectric module were manufactured in the same manner as in Example 2, except that a Ta plating film was not formed on the surface of the CoSb 3 sintered body in Example 2-1, and the Ni plating layer was formed to a thickness of about 5 μm. .
[비교예 3]Comparative Example 3
실시예 2-1에서 CoSb3 소결체의 표면에 Ta 증착막 및 Ni 도금층을 형성하지 않는 것을 제외하고는, 실시예 2와 동일하게 수행하여 열전소자 및 열전모듈을 제조하였다.A thermoelectric device and a thermoelectric module were manufactured in the same manner as in Example 2, except that a Ta deposition film and a Ni plating layer were not formed on the surface of the CoSb 3 sintered body in Example 2-1.
[실험예 2] - 고온 안정성 측정 2Experimental Example 2-High Temperature Stability Measurement 2
본 발명에 따른 열전소자를 이용한 열전모듈의 고온 안정성을 확인하기 위해서, 실시예 2, 비교예 2 및 3에서 각각 제조된 열전모듈을 400 ℃에서 열처리한 다음, FE-SEM을 이용하여 각 모듈의 단면 모습을 확인하였다. 각 열전모듈의 FE-SEM 사진을 도 6 내지 8에 나타내었다.In order to confirm the high temperature stability of the thermoelectric module using the thermoelectric device according to the present invention, the thermoelectric modules manufactured in Example 2, Comparative Examples 2 and 3, respectively, were heat-treated at 400 ° C., and then, FE-SEM of each module was used. The cross section was confirmed. FE-SEM images of each thermoelectric module are shown in FIGS. 6 to 8.
도 6에서 알 수 있는 바와 같이, 실시예 2의 열전모듈은 400 ℃에서의 열처리 후에도 Ta 증착막이 뚜렷하게 존재하였고, 또한 열전반도체 기재인 CoSb3 소결체 내에 합금층이 존재하지 않았다. 이는 열전반도체 기재 내부로 Cu 성분이 Ta 증착막에 의해 확산되지 못한 것으로 추정되었다.As can be seen in FIG. 6, in the thermoelectric module of Example 2, even after the heat treatment at 400 ° C., a Ta deposition film was clearly present, and an alloy layer was not present in the sintered CoSb 3 , which is a thermoelectric semiconductor substrate. It was estimated that the Cu component was not diffused by the Ta deposition film into the thermoelectric semiconductor substrate.
반면, 비교예 2의 열전모듈에는 400 ℃의 열처리 후 CoSb3 소결체 내로 Ni 성분이 확산되여 합금층(도 7의 '☆' 부분 참조)이 형성되어 있었다. 한편, 비교예 3의 열전모듈의 경우, CoSb3 소결체 내부로 솔더 성분인 Sn 성분이 확산되어 합금층(도 8의 '☆' 부분 참조)이 형성되어 있었다.On the contrary, in the thermoelectric module of Comparative Example 2, after the heat treatment at 400 ° C., the Ni component was diffused into the CoSb 3 sintered body to form an alloy layer (see “☆” in FIG. 7). On the other hand, in the thermoelectric module of Comparative Example 3, the Sn component, which is a solder component, was diffused into the CoSb 3 sintered body to form an alloy layer (see '☆' part of FIG. 8).
이와 같이, 본 발명에 따른 확산방지층을 포함하는 열전소자는 400 ℃의 고온에서도 열적 안정성이 우수하다는 것을 확인할 수 있었다.As such, it was confirmed that the thermoelectric device including the diffusion barrier layer according to the present invention had excellent thermal stability even at a high temperature of 400 ° C.
[실험예 3] - 온도 변화에 따른 저항 측정Experimental Example 3-Resistance Measurement According to Temperature Change
실시예 2, 비교예 2 및 3의 열전모듈에 대하여 온도 변화에 따른 저항을 측정하였고, 그 결과를 도 9에 나타내었다.The thermoelectric modules of Example 2, Comparative Examples 2 and 3 were measured for resistance to temperature changes, and the results are shown in FIG. 9.
도 9에 나타난 바와 같이, 320 ℃에서 450 ℃까지 단계적으로 열전모듈의 사용 온도를 올릴 경우, 실시예 2의 열전모듈은 저항이 3.3 Ω에서 3.8 Ω으로 증가하였으나, 저항 변화율은 작았다. 반면, 320 ℃에서 450 ℃까지 단계적으로 사용 온도를 올릴 경우, 비교예 2의 열전모듈은 저항이 3.5 Ω에서 5.7 Ω으로 커졌고, 비교예 3의 열전모듈은 저항이 2.5 Ω에서 12.6 Ω으로 매우 커졌다. 즉, 비교예 2 및 3의 경우, 실시예 2보다 저항 변화율이 컸다.As shown in FIG. 9, when the operating temperature of the thermoelectric module was gradually increased from 320 ° C. to 450 ° C., the resistance of the thermoelectric module of Example 2 increased from 3.3 kW to 3.8 kW, but the resistance change rate was small. On the other hand, when the temperature was raised step by step from 320 ℃ to 450 ℃, the resistance of the thermoelectric module of Comparative Example 2 increased from 3.5 kW to 5.7 kW, and the thermoelectric module of Comparative Example 3 became very large from 2.5 kW to 12.6 kW. . That is, in Comparative Examples 2 and 3, the resistance change rate was larger than that in Example 2.
이와 같이, 본 발명에 따른 확산방지층을 포함하는 열전소자는 사용 온도가 증가하더라도 저항 변화율이 작기 때문에, 열전모듈이 일정한 출력값을 가질 수 있다는 것을 예측할 수 있었다. 또한, 본 발명의 열전소자를 이용한 열전모듈은 고온에서 사용하더라도 저항이 작기 때문에, 열전모듈의 출력값이 커질 수 있다는 것을 예측할 수 있었다.As described above, the thermoelectric device including the diffusion barrier layer according to the present invention has a small resistance change rate even when the use temperature is increased, and thus, the thermoelectric module may have a constant output value. In addition, since the thermoelectric module using the thermoelectric device of the present invention has a low resistance even when used at a high temperature, it can be predicted that the output value of the thermoelectric module may be increased.

Claims (6)

  1. 벌크형 열전반도체 기재; 및Bulk thermoelectric semiconductor substrates; And
    상기 벌크형 열반도체 기재의 표면에, 탄탈늄(Ta), 텅스텐(W), 몰리브덴(Mo) 및 티타늄(Ti)으로 이루어진 군에서 선택된 적어도 하나로 형성된 확산방지층On the surface of the bulk thermal semiconductor substrate, a diffusion barrier layer formed of at least one selected from the group consisting of tantalum (Ta), tungsten (W), molybdenum (Mo) and titanium (Ti).
    을 포함하는 열전소자.Thermoelectric element comprising a.
  2. 제1항에 있어서,The method of claim 1,
    상기 벌크형 열전반도체 기재는 표면조도(Ra)가 0.5 내지 3.0 ㎛ 범위인 것이 특징인 열전소자.The bulk thermoelectric substrate has a surface roughness (Ra) is a thermoelectric element, characterized in that the range of 0.5 to 3.0 ㎛.
  3. 제1항에 있어서,The method of claim 1,
    상기 확산방지층은 두께가 0.3 내지 20 ㎛ 범위인 것이 특징인 열전소자.The diffusion barrier layer is characterized in that the thickness of 0.3 to 20 ㎛ range.
  4. 제1항에 있어서,The method of claim 1,
    상기 확산방지층 위에 형성된 니켈(Ni)층을 더 포함하는 것이 특징인 열전소자.The thermoelectric device, characterized in that it further comprises a nickel (Ni) layer formed on the diffusion barrier layer.
  5. 제1항에 있어서,The method of claim 1,
    열전발전용인 것이 특징인 열전소자.A thermoelectric element characterized by being exclusively for thermo development.
  6. 제1항 내지 제5항 중 어느 한 항에 따른 열전소자를 포함하는 열전모듈.A thermoelectric module comprising the thermoelectric element according to any one of claims 1 to 5.
PCT/KR2017/009227 2016-08-23 2017-08-23 Thermoelectric element and thermoelectric module comprising same WO2018038540A1 (en)

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Publication number Priority date Publication date Assignee Title
KR20120086190A (en) * 2011-01-25 2012-08-02 엘지이노텍 주식회사 Thermoelectric Device using Bulk Material of Nano Structure and Thermoelectric Module having The Same, and Method of Manufacture The Same
JP2014086623A (en) * 2012-10-25 2014-05-12 Furukawa Co Ltd Thermoelectric conversion module
KR101439461B1 (en) * 2013-11-08 2014-09-17 한국기계연구원 A Thermolectric Semiconductor module and A Manufacturing Method of The same
KR20140140905A (en) * 2013-05-30 2014-12-10 주식회사 엘지화학 Manufacturing Method of Thermoelectric Film
KR20160013309A (en) * 2014-07-24 2016-02-04 주식회사 제펠 Thermoelectric module having sintered layer and method of manufacturing the module

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20120086190A (en) * 2011-01-25 2012-08-02 엘지이노텍 주식회사 Thermoelectric Device using Bulk Material of Nano Structure and Thermoelectric Module having The Same, and Method of Manufacture The Same
JP2014086623A (en) * 2012-10-25 2014-05-12 Furukawa Co Ltd Thermoelectric conversion module
KR20140140905A (en) * 2013-05-30 2014-12-10 주식회사 엘지화학 Manufacturing Method of Thermoelectric Film
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