WO2018143780A1 - 열전 소자 - Google Patents

열전 소자 Download PDF

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Publication number
WO2018143780A1
WO2018143780A1 PCT/KR2018/001590 KR2018001590W WO2018143780A1 WO 2018143780 A1 WO2018143780 A1 WO 2018143780A1 KR 2018001590 W KR2018001590 W KR 2018001590W WO 2018143780 A1 WO2018143780 A1 WO 2018143780A1
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WIPO (PCT)
Prior art keywords
thermoelectric
substrate
disposed
electrode portion
region
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Ceased
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PCT/KR2018/001590
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English (en)
French (fr)
Korean (ko)
Inventor
성명석
김태희
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LG Innotek Co Ltd
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LG Innotek Co Ltd
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Application filed by LG Innotek Co Ltd filed Critical LG Innotek Co Ltd
Priority to US16/482,522 priority Critical patent/US11937506B2/en
Priority to CN201880010507.1A priority patent/CN110268536B/zh
Priority to JP2019540635A priority patent/JP7293116B2/ja
Publication of WO2018143780A1 publication Critical patent/WO2018143780A1/ko
Anticipated expiration legal-status Critical
Priority to US18/443,637 priority patent/US12274171B2/en
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/10—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects
    • H10N10/17—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects characterised by the structure or configuration of the cell or thermocouple forming the device
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/01—Manufacture or treatment
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/80—Constructional details
    • 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
    • H10N10/81—Structural details of the junction
    • 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
    • H10N10/82—Interconnections
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/80—Constructional details
    • H10N10/85—Thermoelectric active materials
    • H10N10/851—Thermoelectric active materials comprising inorganic compositions
    • H10N10/852—Thermoelectric active materials comprising inorganic compositions comprising tellurium, selenium or sulfur

Definitions

  • Embodiments relate to thermoelectric devices.
  • Thermoelectric phenomenon is a phenomenon caused by the movement of electrons and holes in a material, and means a direct energy conversion between heat and electricity.
  • thermoelectric element is a generic term for a device using a thermoelectric phenomenon, and has a structure in which a P-type thermoelectric material and an N-type thermoelectric material are bonded between metal electrodes to form a PN junction pair.
  • Thermoelectric elements may be classified into a device using a temperature change of the electrical resistance, a device using the Seebeck effect, a phenomenon in which electromotive force is generated by the temperature difference, a device using a Peltier effect, a phenomenon in which endothermic or heat generation by current occurs. .
  • thermoelectric devices have been applied to a variety of home appliances, electronic components, communication components and the like.
  • the thermoelectric element may be applied to a cooling device, a heating device, a power generating device, or the like. Accordingly, the demand for thermoelectric performance of thermoelectric elements is increasing.
  • thermoelectric element may receive a current through a wiring electrode, that is, a terminal wire, and for example, the wiring electrode may be connected to an electrode layer of the thermoelectric element on an upper or lower substrate.
  • thermoelectric element becomes smaller, a poor connection between the wiring electrode and the electrode layer may increase.
  • a method of forming a terminal pad portion on a substrate instead of a wiring electrode and connecting it to an external circuit by soldering may be used.
  • the external substrate since the external substrate must be formed wide, there is a problem in that the total area of the device becomes wider and the performance compared to the area decreases.
  • a method of disposing a post (metal pillar) on the lower substrate instead of the terminal wire and then wire-bonding the external power supply and the thermoelectric element through the wiring electrode may be used.
  • the external power source and the thermoelectric element may be wire-bonded through the wiring electrode on the upper substrate.
  • the wiring electrode since the wiring electrode is disposed at the portion acting as the heat absorbing portion, it may occur due to the supply of current. The problem that the performance of the heat absorbing portion is deteriorated by heat or heat generated from the wiring electrode may occur.
  • thermoelectric device having a new structure that can solve the above problems.
  • Embodiments provide a thermoelectric device capable of preventing poor terminal wire bonding and realizing miniaturization with improved efficiency.
  • the thermoelectric device includes a first substrate; A first electrode part disposed on the first substrate; A thermoelectric semiconductor disposed on the first electrode portion; A second electrode portion disposed on the thermoelectric semiconductor; And a second substrate disposed on the second electrode portion, wherein the second substrate comprises: a first surface; And a second surface facing the first surface, wherein the second electrode portion is disposed on the first surface, and the terminal electrode portion is formed on the second surface to extend at least one of the second electrode portions. And the second substrate is formed between the terminal electrode portion and the second electrode portion.
  • thermoelectric element according to the embodiment may reduce the heat moving in the direction of the second electrode portion from the terminal electrode portion.
  • thermoelectric device may be formed through the through hole and the buffer member filled in the through hole. By separating the portion from the second electrode portion, the amount of heat moved in the direction of the second electrode portion can be reduced.
  • the thickness of the region where the terminal electrode portion is disposed may be larger than the thickness of the region where the second electrode portion is disposed.
  • the thermal conductivity of the region where the terminal electrode portion is disposed may be lower than the thermal conductivity of the region where the second electrode portion is disposed. In addition, it is possible to reduce the heat transfer in the vertical direction in the region where the terminal electrode portion is disposed.
  • thermoelectric element when bonding the terminal electrode portion and the wiring electrode by the stepped portion of the region where the terminal electrode portion is disposed, mechanical shock caused by the step difference with the frame can be alleviated, thereby improving the reliability of the thermoelectric element.
  • thermoelectric device 1 is a cross-sectional view of a thermoelectric device according to example embodiments.
  • thermoelectric device 2 is a plan view illustrating a lower substrate of the thermoelectric device according to the first embodiment.
  • thermoelectric device 3 is a plan view illustrating an upper substrate of the thermoelectric device according to the first embodiment.
  • FIG. 4 is an enlarged view illustrating an enlarged area A of FIG. 3.
  • thermoelectric device illustrates partial cross-sectional views of the thermoelectric device according to the first embodiment.
  • thermoelectric element 7 illustrates a plan view of an upper substrate of a thermoelectric element according to a second embodiment.
  • FIG. 8 is an enlarged view illustrating an enlarged area B of FIG. 7.
  • thermoelectric device 9 and 10 are partial cross-sectional views of a thermoelectric device according to a second embodiment.
  • thermoelectric device 11 and 12 illustrate partial cross-sectional views of a thermoelectric device according to a third exemplary embodiment.
  • thermoelectric 13 is a partial cross-sectional view of a conventional thermoelectric device.
  • thermoelectric legs of a laminated structure illustrate thermoelectric legs of a laminated structure.
  • thermoelectric leg sintered body 17 is a view showing a process flow for manufacturing a thermoelectric leg sintered body according to the embodiment.
  • ordinal numbers such as second and first
  • first and second components may be used to describe various components, but the components are not limited by the terms. The terms are used only for the purpose of distinguishing one component from another.
  • second component may be referred to as the first component, and similarly, the first component may also be referred to as the second component.
  • thermoelectric element 1 is a diagram illustrating a cross section of a thermoelectric element included in embodiments.
  • the thermoelectric element 100 may include a first substrate 110, a second substrate 120, a first electrode portion 210, and a second electrode portion 220 thermoelectric semiconductor 300.
  • the thermoelectric semiconductor 300 may include a first thermoelectric semiconductor 310 and a second thermoelectric semiconductor 320.
  • the first substrate 110 may be a lower substrate
  • the second substrate 120 may be an upper substrate disposed on the first substrate 110.
  • the first electrode unit 210 may be disposed between the first substrate 110, the lower bottom surface of the first thermoelectric semiconductor 310, and the second thermoelectric semiconductor 320.
  • the second electrode unit 220 may be disposed between the second substrate 120, the upper bottom surface of the first thermoelectric semiconductor 310, and the second thermoelectric semiconductor 320.
  • the plurality of first thermoelectric semiconductors 310 and the plurality of second thermoelectric semiconductors 320 may be electrically connected by the first electrode part 210 and the second electrode part 220.
  • a pair of the first thermoelectric semiconductor 310 and the second thermoelectric semiconductor 320 disposed between the first electrode 210 and the second electrode 220 and electrically connected to each other is a unit cell. Can be formed.
  • thermoelectric semiconductor 310 when a voltage is applied to the first electrode portion 210 and the second electrode portion 220 through a wiring, due to the Peltier effect, from the first thermoelectric semiconductor 310 to the second thermoelectric semiconductor 320.
  • the first substrate 110 may act as a heat generating unit
  • the second substrate 120 may act as a cooling unit.
  • the first thermoelectric semiconductor 310 and the second thermoelectric semiconductor 320 may include a P-type thermoelectric leg and an N-type thermoelectric leg, respectively.
  • the first thermoelectric semiconductor 310 may include a P-type thermoelectric leg
  • the second thermoelectric semiconductor 320 may include an N-type thermoelectric leg.
  • thermoelectric semiconductor 310 and the second thermoelectric semiconductor 320 may be bismuth fluoride (Bi-Te) -based thermoelectric legs including bismuth (Bi) and tellurium (Te) as main materials.
  • the first thermoelectric semiconductor 310 has antimony (Sb), nickel (Ni), aluminum (Al), copper (Cu), silver (Ag), lead (Pb), and boron based on a total weight of 100 wt%.
  • the main raw material is Bi-Sb-Te, and may further include Bi or Te as 0.001wt% to 1wt% of the total weight.
  • the second thermoelectric semiconductor 320 is selenium (Se), nickel (Ni), aluminum (Al), copper (Cu), silver (Ag), lead (Pb), boron (B), Bismuth fluoride (Bi-Te) -based main raw material material containing at least one of gallium (Ga), tellurium (Te), bismuth (Bi) and indium (In) 99wt% to 99.999wt% and Bi or Te And thermoelectric legs comprising 0.001 wt% to 1 wt% of the mixture.
  • the main raw material is Bi-Se-Te, and may further include Bi or Te as 0.001wt% to 1wt% of the total weight.
  • the first thermoelectric semiconductor 310 and the second thermoelectric semiconductor 320 may be formed in a bulk type or a stacked type.
  • the first bulk thermoelectric semiconductor 310 or the second bulk thermoelectric semiconductor 320 is manufactured by heating a thermoelectric material to manufacture an ingot, and pulverizing and sieving the ingot to obtain powder for thermoelectric legs. Sintering, and can be obtained through the process of cutting the sintered body.
  • the stacked first thermoelectric semiconductor 310 or the stacked second thermoelectric semiconductor 320 is formed by applying a paste including a thermoelectric material on a sheet-shaped substrate to form a unit member, and then stacking and cutting the unit members. Can be obtained.
  • the pair of first thermoelectric semiconductor 310 and the second thermoelectric semiconductor 320 may have the same shape and volume or may have different shapes and volumes.
  • the height or the cross-sectional area of the second thermoelectric semiconductor 320 may be the height or the cross-sectional area of the first thermoelectric semiconductor 310. It can also be formed differently.
  • thermoelectric device The performance of the thermoelectric device according to the exemplary embodiment of the present invention may be represented by Seebeck index.
  • the Seebeck index ZT may be expressed as in Equation 1.
  • ⁇ is the Seebeck coefficient [V / K]
  • sigma is the electrical conductivity [S / m]
  • ⁇ 2 sigma is the Power Factor [W / mK 2].
  • T is the temperature and k is the thermal conductivity [W / mK].
  • k can be expressed as acp, a is the thermal diffusivity [cm2 / S], cp is the specific heat [J / gK], and ⁇ is the density [g / cm3].
  • the Z value (V / K) may be measured using a Z meter, and the Seebeck index (ZT) may be calculated using the measured Z value.
  • first electrode portion 210, the second substrate 12, and the second substrate 12 disposed between the first substrate 110, the first thermoelectric semiconductor 310, and the second thermoelectric semiconductor 320.
  • the second electrode part 220 disposed between the first thermoelectric semiconductor 310 and the second thermoelectric semiconductor 320 includes at least one of copper (Cu), silver (Ag), and nickel (Ni). It may have a thickness of 0.01mm to 0.3mm.
  • the thickness of the first electrode portion 210 or the second electrode portion 220 is less than 0.01mm, the function of the electrode is reduced, the electrical conduction performance can be lowered, if it exceeds 0.3mm due to the increase in resistance Conduction efficiency can be lowered.
  • first substrate 110 and the second substrate 120 that face each other may be an insulating substrate or a metal substrate.
  • the insulating substrate may be an alumina substrate or a polymer resin substrate having flexibility.
  • Flexible polymer resin substrates are highly permeable, such as polyimide (PI), polystyrene (PS), polymethyl methacrylate (PMMA), cyclic olefin copoly (COC), polyethylene terephthalate (PET), and resin
  • PI polyimide
  • PS polystyrene
  • PMMA polymethyl methacrylate
  • COC cyclic olefin copoly
  • PET polyethylene terephthalate
  • resin Various insulating resin materials, such as plastics can be included.
  • the metal substrate may comprise Cu, Cu alloy or Cu—Al alloy, and the thickness may be 0.1 mm to 0.5 mm.
  • the thickness of the metal substrate is less than 0.1 mm or exceeds 0.5 mm, the heat dissipation characteristics or the thermal conductivity may be too high, so that the reliability of the thermoelectric element may be lowered.
  • first substrate 110 and the second substrate 120 is a metal substrate
  • between the first substrate 110 and the first electrode portion 210 and between the second substrate 120 and the Dielectric layers 170 may be further disposed between the second electrode parts 220.
  • the dielectric layer 170 may include a material having a thermal conductivity of 5 to 10 W / K, and may be formed to a thickness of 0.01 mm to 0.15 mm. When the thickness of the dielectric layer 170 is less than 0.01 mm, insulation efficiency or withstand voltage characteristics may be reduced, and when the thickness of the dielectric layer 170 is greater than 0.15 mm, thermal conductivity may be lowered to reduce heat radiation efficiency.
  • the size of the first substrate 110 and the second substrate 120 may be formed differently.
  • the volume, thickness, or area of one of the first substrate 110 and the second substrate 120 may be greater than the volume, thickness, or area of the other.
  • a heat radiation pattern for example, an uneven pattern may be formed on at least one surface of the first substrate 110 and the second substrate 120.
  • the heat dissipation performance of a thermoelectric element can be improved.
  • the uneven pattern is formed on the surface in contact with the first thermoelectric semiconductor 310 or the second thermoelectric semiconductor 320, the bonding property between the thermoelectric leg and the substrate may also be improved.
  • FIGS. 2 to 4 are plan views of the first substrate 210 and the second substrate 120 in the thermoelectric device according to the first embodiment
  • FIGS. 5 and 6 are views according to the first embodiment. It is a figure which shows sectional drawing of a thermoelectric element.
  • a plurality of first electrode parts 210 may be disposed on the first substrate 110.
  • the first electrode portions 210 may be disposed with a pattern on one surface of the first substrate 110. That is, a plurality of first electrode patterns spaced apart from each other may be disposed on one surface of the first substrate 110.
  • thermoelectric semiconductor 310 and / or the second thermoelectric semiconductor 320 described above may be disposed on the plurality of first electrode patterns.
  • the first substrate 110 may be a substrate in which current flows from the second thermoelectric semiconductor 320 to the first thermoelectric semiconductor 310 and serves as a heat generating unit.
  • a plurality of second electrode parts 220 may be disposed on the second substrate 120.
  • the second electrode parts 220 may be disposed with a pattern on one surface of the second substrate 120. That is, a plurality of second electrode patterns spaced apart from each other may be disposed on one surface of the second substrate 120.
  • thermoelectric semiconductor 310 and / or the second thermoelectric semiconductor 320 described above may be disposed on the plurality of second electrode patterns.
  • the second substrate 120 may be a substrate that serves as a cooling unit as a substrate through which current flows from the first thermoelectric semiconductor 310 to the second thermoelectric semiconductor 320.
  • the second substrate 120 may include a first surface 121 and a second surface 122.
  • the second substrate 120 may include the first surface 121 and the second surface 122 opposite to the first surface 121.
  • the second substrate 120 may include the first surface 121 and a second surface 122 facing the first surface 121.
  • thermoelectric chip 800 may be disposed on the second substrate 120.
  • a separate substrate may be further disposed on the second substrate, and a thermoelectric chip 800 may be mounted on the separate substrate. That is, a thermoelectric chip mount substrate may be disposed on the second substrate 120.
  • the thermoelectric device according to the first embodiment may include a terminal electrode part 400.
  • the terminal electrode part 400 may be an electrode connected to an external wiring.
  • the terminal electrode part 400 may be an area where a voltage is applied through the wiring electrode 500 from the supply part 510 disposed on the outer frame 600.
  • the terminal electrode part 400 may be disposed to extend in one direction, for example, in a lateral direction, from at least one second electrode part 220 of the second electrode parts 220. In detail, the terminal electrode part 400 may be disposed in contact with the second electrode part 220. In detail, the terminal electrode part 400 may be integrally formed with the second electrode part 220. In detail, the terminal electrode part 400 may be formed of the same material as the second electrode part 200.
  • the second electrode part 220 may be a region in which a thermoelectric semiconductor is disposed, and a region in which the thermoelectric semiconductor is not disposed in the terminal electrode portion 400.
  • the terminal electrode part 400 may be disposed in an edge region of the second substrate 120.
  • the terminal electrode part 400 may be disposed in an edge region of the second substrate 120.
  • the terminal electrode part 400 extends in one direction from the second electrode part 220, and the terminal electrode part 400 is a first surface of the second substrate 120. It may be disposed on the 121 and the second surface 122.
  • connection hole CH may be formed in the second substrate 120.
  • connection hole CH may be formed on an area overlapping with an area where the terminal electrode part 400 and the second electrode part 220 are in contact with each other.
  • the terminal electrode part 400 may extend from the first surface 121 of the second substrate 110 to the second surface 122 through the connection hole CH. That is, the terminal electrode part 400 is disposed on the first surface 121 and the second surface 122 of the second substrate 120, and the first surface 121 and the second surface ( The terminal electrode part 400 disposed in the 122 may be connected by the terminal electrode part 400 disposed in the connection hole CH.
  • a through hole H may be formed in the second substrate 120.
  • the through hole H may be disposed between the terminal electrode part 400 and the second electrode part 220.
  • the through hole H may be formed between the second electrode portion 220 and the terminal electrode portion 400 other than the second electrode portion 220 in contact with the terminal electrode portion 400. have.
  • the through hole H may extend along side surfaces of the terminal electrode part 400 and the second electrode part 220 in contact with the terminal electrode part 400.
  • the through hole H may extend from one side of the second substrate 120 in the other side direction.
  • the width W of the through hole H may be different from the distance D between the terminal electrode part 400 and the second electrode part 220 that is closest to the terminal electrode part 400.
  • the width W of the through hole H is different from the second electrode part 220 other than the second electrode part 220 in contact with the terminal electrode part 400 and the terminal electrode part 400. It may be less than the distance (D) between.
  • the ratio of the width W of the through hole H and the distance D between the terminal electrode part 400 and the second electrode part 220 closest to each other may be 0.4: 1 to 0.6: 1. have. That is, the size of the width W of the through hole H is about 40% to 60% of the size of the distance D between the terminal electrode part 400 and the second electrode part 220 closest to each other. Can be.
  • the terminal electrode part Cooling performance may be degraded by heat transferred toward the second electrode portion 220 in the region where the 400 is disposed.
  • the width W of the through hole H exceeds about 60% with respect to the size of the distance D between the terminal electrode part 400 and the second electrode part 220 closest to each other, The strength of the second substrate 120 may decrease.
  • the heat generated from the terminal electrode part 400 by the through hole H may be reduced in the direction of the second electrode part 220 adjacent to the terminal electrode part 400. That is, heat generated in the terminal electrode part 400 in which the wiring electrode 500 is disposed may move in the direction of the second electrode part 220, but the thermoelectric device according to the embodiment may include the through-hole H.
  • the thermoelectric device according to the embodiment may include the through-hole H.
  • a buffer member 700 may be disposed in the through hole H.
  • a buffer member 700 including a resin material or a polymer material may be disposed in the through hole H.
  • the buffer member 700 may include a material having low thermal conductivity.
  • the buffer member 700 may include a material having low thermal conductivity such as polyimide or parylene.
  • the buffer member 700 may be disposed in the through hole H.
  • the buffer member 700 may be filled in the through hole H.
  • the buffer member 700 may be disposed while filling the inside of the through hole H.
  • the buffer member 700 may be disposed inside the through hole H to prevent a decrease in strength of the second substrate 120 on which the through hole H is formed.
  • the buffer member 700 may relieve stress caused by contraction or expansion of the second substrate, which may occur in the region where the temperature change of the substrate is greatest by the terminal electrode 400 in the second substrate 120. The reliability of the whole thermoelectric element can be improved.
  • thermoelectric device according to the second embodiment will be described with reference to FIGS. 7 to 10.
  • thermoelectric element according to the second embodiment descriptions similar to those of the thermoelectric element according to the first embodiment will be omitted and the same reference numerals will be given to the same components.
  • connection hole CH may not be formed.
  • the second substrate 120 may include the first surface 121, the second surface 122, and the third surface 123.
  • the third surface 123 may be a surface connecting the first surface 121 and the second surface 122.
  • the third surface 123 may be a side surface of the second substrate 120.
  • the terminal electrode part 400 may extend from the first surface 121 of the second substrate 120 to the three surfaces 123 and the second surface 122. That is, the terminal electrode part 400 may extend from the first surface 121 of the second substrate 120 to the second surface 122 through the third surface 123.
  • a process of forming a separate connection hole for connecting the terminal electrode part to the second substrate 120 may be omitted. Accordingly, it is possible to prevent the strength of the second substrate 120 from being lowered by the connection hole, thereby improving overall reliability of the thermoelectric device and improving process efficiency.
  • thermoelectric devices according to the Examples and Comparative Examples. These examples are merely given to illustrate the present invention in more detail. Therefore, the present invention is not limited to these examples.
  • a second electrode portion and a terminal electrode are disposed on a second substrate, a through hole is formed between the second electrode portion and the terminal electrode to manufacture a thermoelectric element, and then the terminal electrode and the wiring electrode are connected to supply a voltage. After application, the amount of heat transfer to the second electrode portion was measured.
  • thermoelectric device was manufactured in the same manner as in Example 1 except that the through hole was filled with polyimide, and then the terminal electrode and the wiring electrode were connected to apply a voltage, and then moved to the second electrode part. The heat transfer amount was measured.
  • thermoelectric device was manufactured in the same manner as in Example 1 except that a through hole was not formed, and then a voltage was applied by connecting the terminal electrode and the wiring electrode and measuring the amount of heat transfer to the second electrode unit. It was.
  • Example 1 Example 2 Comparative Example 1 Heat transfer (mW) 1.9 0.08 43
  • thermoelectric elements according to the first and second embodiments the heat transferred from the terminal electrode part to the second electrode part is smaller than that of the thermoelectric device according to Comparative Example 1.
  • the heat transferred from the terminal electrode portion to the second electrode portion may be less than about 5% of the thermoelectric element according to Comparative Example 1.
  • thermoelectric device can reduce the heat transferred from the terminal electrode part to the second electrode part by the through hole and the buffer member filled in the through hole.
  • thermoelectric device according to the third embodiment will be described with reference to FIGS. 11 and 12.
  • the description of the same and similar descriptions as those of the first and second embodiments described above will be omitted, and the same reference numerals will be given to the same configuration.
  • the thickness of the second substrate 120 may be different for each region.
  • the second substrate 120 may include a first region 1A and a second region 2A.
  • the first region 1A may be a region in which the second electrode unit 220 is disposed.
  • the first region 1A may be defined as a region in which the second electrode unit 220 in which the thermoelectric semiconductors 310 and 320 are disposed is disposed.
  • the second area 2A may be an area where the terminal electrode part 400 is disposed.
  • the second area 2A may be defined as an area in which the terminal electrode part 400 in which the thermoelectric semiconductors 310 and 320 are not disposed is disposed.
  • the first region 1A and the second region 2A may be in contact with each other.
  • the first region 1A and the second region 2A may include the same material.
  • the first region 1A and the second region 2A may be integrally formed.
  • the thickness of the first region 1A and the thickness of the second region 2A may be different.
  • the thickness of the first region 1A may be smaller than the thickness of the second region 2A. That is, the thickness of the second region 2A may be greater than the thickness of the first region 1A.
  • the thickness of the second region 2A on which the terminal electrode portion 400 is disposed may be thicker than the thickness of the first region 1A on which the second electrode portion 220 is disposed.
  • the second region 2A may include a stepped portion 125.
  • the first region 1A and the second region 2A may have a step by the step portion 125.
  • the thickness of the second region 2A may be greater than the thickness of the first region 1A by the step portion 125.
  • the height h1 of the thermoelectric chip 800 may be equal to or less than the height h2 of the stepped part 125. That is, the height h1 of the thermoelectric chip 800 may be equal to or smaller than the height h2 of the stepped part 125. In this case, the height h1 of the thermoelectric chip 800 is a distance from one surface of the thermoelectric chip 800 facing the second substrate to the other surface opposite to the one surface in the first region 1A.
  • the height of the stepped part 125 may be defined as the distance from one surface of the stepped part 125 facing the second substrate to the other surface opposite to the one surface in the second area 2A. have.
  • thermoelectric chip 800 may be reduced, so that the thermoelectric element may be easily coupled with another module.
  • the thickness T2 of the second region 2A may be about 0.5 to about 3 times larger than the thickness T1 of the first region 1A. In detail, the thickness T2 of the second region 2A may be about 1.5 times to about 3 times larger than the thickness T1 of the first region 1A.
  • the thickness T2 of the second region 2A has a size less than about 0.5 times the thickness T1 of the first region 1A, the wiring electrode 500 and the terminal electrode 400 It is not possible to effectively reduce heat transfer in the generated vertical direction.
  • the thickness T2 of the second region 2A has a size exceeding about three times the thickness T1 of the first region 1A, the process efficiency may decrease.
  • the first region 1A and the second region 2A may have different thermal conductivity.
  • the thermal conductivity of the second region 2A may be smaller than that of the first region 1A.
  • the second region 2A may have anisotropic thermal conductivity.
  • the vertical thermal conductivity of the second region 2A may be about 30% or less. That is, the second region 2A may reduce the thermal conductivity in the vertical direction.
  • the second region 2A may include a ceramic material.
  • the second region 2A may include a boron nitride (BN) material.
  • the ceramic material may be disposed in the entirety of the second region 2A or only in the stepped portion 125 of the second region 2A.
  • the thickness of the region where the terminal electrode portion is disposed may be greater than the thickness of the region where the second electrode portion is disposed.
  • the thermal conductivity of the region where the terminal electrode portion is disposed may be lower than the thermal conductivity of the region where the second electrode portion is disposed.
  • thermoelectric element when bonding the terminal electrode portion and the wiring electrode by the stepped portion of the region where the terminal electrode portion is disposed, mechanical shock caused by the step difference with the frame can be alleviated, thereby improving the reliability of the thermoelectric element.
  • thermoelectric devices according to the Examples and Comparative Examples. These examples are merely given to illustrate the present invention in more detail. Therefore, the present invention is not limited to these examples.
  • the second electrode portion is disposed in the region where the stepped portion is not disposed, the terminal electrode is disposed in the region where the stepped portion is disposed, and a thermoelectric element is manufactured. After applying the voltage, the amount of heat transfer to the second electrode portion was measured.
  • thermoelectric device was manufactured in the same manner as in Example 1, the voltage was transferred by connecting the terminal electrode and the wiring electrode, and then the amount of heat transfer to the second electrode was measured. .
  • Example 3 Comparative Example 2 Heat transfer (mW) 0.5 17
  • thermoelectric device according to Example 3 it can be seen that the heat transferred from the terminal electrode part to the second electrode part is smaller than that of the thermoelectric device according to Comparative Example 2.
  • thermoelectric device according to Example 3 it can be seen that heat transferred from the terminal electrode part to the second electrode part is less than about 3% of the thermoelectric device according to Comparative Example 2.
  • thermoelectric element according to the embodiment can reduce the heat transferred from the terminal electrode portion to the second electrode portion by the stepped portion.
  • thermoelectric elements such as an optical communication laser module are disposed in the central region of the module
  • thermoelectric elements it is difficult to connect an electrode layer between a wiring electrode, that is, a terminal electrode and a thermoelectric element.
  • a wiring electrode that is, a terminal electrode and a thermoelectric element.
  • wire bonding to the terminal electrode is not easy because various components are mounted.
  • a post 900 that is, a metal pillar, is disposed on a lower substrate, and an external power source and an electrode layer of a thermoelectric element are connected.
  • the area of the lower substrate becomes larger than that of the upper substrate and the thermoelectric semiconductor cannot be disposed on the widened lower substrate, it is disadvantageous in miniaturization and efficiency can be reduced compared to the area.
  • thermoelectric device can prevent the terminal wire bonding failure, and can implement a miniaturized thermoelectric device with improved efficiency.
  • thermoelectric device may reduce the heat moving in the direction of the second electrode portion from the terminal electrode portion.
  • thermoelectric device may be formed through the through hole and the buffer member filled in the through hole. By separating the portion from the second electrode portion, the amount of heat moved in the direction of the second electrode portion can be reduced.
  • the thickness of the region where the terminal electrode portion is disposed may be larger than the thickness of the region where the second electrode portion is disposed.
  • the thermal conductivity of the region where the terminal electrode portion is disposed may be lower than the thermal conductivity of the region where the second electrode portion is disposed. In addition, it is possible to reduce the heat transfer in the vertical direction in the region where the terminal electrode portion is disposed.
  • thermoelectric element when bonding the terminal electrode portion and the wiring electrode by the stepped portion of the region where the terminal electrode portion is disposed, mechanical shock caused by the step difference with the frame can be alleviated, thereby improving the reliability of the thermoelectric element.
  • thermoelectric device may be wire-bonded on the upper substrate instead of the lower substrate while miniaturization, so that an additional thermoelectric semiconductor may be disposed in the bonding region, thereby improving thermoelectric efficiency.
  • thermoelectric device may reduce the step of the wire bonding, thereby reducing the bonding failure, it may have improved reliability.
  • thermoelectric leg of the thermoelectric device may have a stacked structure.
  • the P-type thermoelectric leg or the N-type thermoelectric leg may be formed by stacking a plurality of structures coated with a semiconductor material on a sheet-shaped substrate and then cutting them. As a result, it is possible to prevent loss of material and to improve electrical conduction characteristics.
  • thermoelectric leg 14 shows a method of making a thermoelectric leg of a laminated structure.
  • a material including a semiconductor material is prepared in the form of a paste, and then coated on a substrate 1110 such as a sheet or a film to form a semiconductor layer 1120. Accordingly, one unit member 1100 may be formed.
  • a plurality of unit members 1100a, 1100b, and 1100c may be stacked to form the stacked structure 1200, and the unit thermoelectric legs 1300 may be obtained by cutting the stacked structures 1200.
  • the unit thermoelectric leg 1300 may be formed by a structure in which a plurality of unit members 1100 having the semiconductor layer 1120 formed on the substrate 1110 are stacked.
  • the process of applying the paste on the substrate 1110 may be performed in various ways.
  • Tape casting method is a slurry by mixing a fine semiconductor material powder with at least one selected from an aqueous or non-aqueous solvent, binder, plasticizer, dispersant, defoamer and surfactant
  • the preparation in the form (slurry) it is a method of molding on a moving blade (blade) or a moving substrate.
  • the substrate 1110 may be a film, a sheet, or the like having a thickness of 10 ⁇ m to 100 ⁇ m, and the P-type thermoelectric material or the N-type thermoelectric material for manufacturing the bulk type device may be applied as it is.
  • the step of arranging the unit members 1100 in a plurality of layers may be performed by pressing at a temperature of 50 ° C. to 250 ° C., and the number of stacked unit members 110 may be, for example, 2 to 50 days. Can be. Thereafter, it may be cut into a desired shape and size, and a sintering process may be added.
  • the unit thermoelectric leg 1300 manufactured as described above may secure uniformity in thickness, shape, and size, and may be advantageously thinned and may reduce material loss.
  • the unit thermoelectric leg 1300 may have a cylindrical shape, a polygonal column shape, an elliptical column shape, or the like, and may be cut into a shape as illustrated in FIG. 14 (d).
  • thermoelectric leg having a stacked structure a thermoelectric leg having a stacked structure
  • a conductive layer may be further formed on one surface of the unit member 1100.
  • FIG. 15 illustrates a conductive layer formed between unit members in the stacked structure of FIG. 14.
  • the conductive layer C may be formed on an opposite side of the substrate 1110 on which the semiconductor layer 1120 is formed, and may be patterned to expose a portion of the surface of the substrate 1110.
  • FIG. 15 shows various modifications of the conductive layer C according to the embodiment of the present invention.
  • a mesh type structure including closed opening patterns c1 and c2, or as shown in Figs. 15C and 15D, Various modifications may be made to a line type structure including the open opening patterns c3 and c4.
  • the conductive layer (C) can increase the adhesive force between the unit members in the unit thermoelectric leg formed in a laminated structure of the unit member, lower the thermal conductivity between the unit members, it is possible to improve the electrical conductivity.
  • the conductive layer C may be a metal material, for example, Cu, Ag, Ni, or the like.
  • the unit thermoelectric leg 1300 may be cut in the direction as shown in FIG. 16. According to this structure, it is possible to reduce the thermal conductivity in the vertical direction and to improve the electrical conductivity, thereby increasing the cooling efficiency.
  • thermoelectric leg may be manufactured by a zone melting method or a powder sintering method.
  • zone melting method an ingot is manufactured by using a thermoelectric material, and then, by slowly applying heat to the ingot, the particles are rearranged so as to be rearranged in a single direction, and the thermoelectric leg is slowly cooled.
  • powder sintering method after manufacturing an ingot using a thermoelectric material, the ingot is pulverized and sieved to obtain a thermoelectric leg powder, and the thermoelectric leg is obtained through the sintering process.
  • thermoelectric leg sintered body 17 is a flowchart illustrating a method of manufacturing a thermoelectric leg sintered body according to an embodiment of the present invention.
  • thermoelectric material is heat treated to produce an ingot (S100).
  • Thermoelectric materials may include Bi, Te and Se.
  • the thermoelectric material may include Bi2Te3-ySey (0.1 ⁇ y ⁇ 0.4).
  • the vapor pressure of Bi is 10 Pa at 768 ° C
  • the vapor pressure of Te is 104 Pa at 769 ° C
  • the steam pressure of Se is 105 Pa at 685 ° C. Therefore, the vapor pressure of Te and Se is high at general melting temperature (600-800 degreeC), and volatility is large. Therefore, the thermoelectric leg may be weighed in consideration of volatilization of at least one of Te and Se.
  • Te and Se may be further included in 1 to 10 parts by weight.
  • 1 to 10 parts by weight of Te and Se may be further included with respect to 100 parts by weight of Bi2Te3-ySey (0.1 ⁇ y ⁇ 0.4).
  • the ingot is crushed (S110).
  • the ingot may be pulverized according to a melt spinning technique.
  • a thermoelectric material of plate flakes can be obtained.
  • thermoelectric material of the plate-shaped flake is milled together with the doping additive (S120).
  • the doping additive for example, a super mixer, a ball mill, an attention mill, a 3 roll mill, or the like may be used.
  • the doping additive may include, for example, Cu and Bi2O3.
  • thermoelectric material containing Bi, Te and Se is 99.4 to 99.98wt%
  • Cu is 0.01 to 0.1wt%
  • Bi2O3 is 0.01 to 0.5wt% of the composition ratio, preferably Bi, Te and Se
  • the thermoelectric material is 99.48 to 99.98wt%
  • Cu is 0.01 to 0.07wt%
  • Bi2O3 is 0.01 to 0.45wt% composition ratio, more preferably 99.67 to 99.98wt%
  • Cu containing Bi, Te and Se Cu Is 0.01 to 0.03wt%
  • Bi2O3 may be milled after being added at a composition ratio of 0.01 to 0.30wt%.
  • thermoelectric leg powder is obtained through sieving (S130).
  • the sieving process is added as needed, and is not an essential process in the embodiment of the present invention.
  • the thermoelectric leg powder may have, for example, a particle size in micro units.
  • thermoelectric leg powder is sintered (S140).
  • the sintered body obtained by the sintering process can be cut to produce a thermoelectric leg.
  • Sintering is performed for 1 to 30 minutes at 400 to 550 ° C., 35 to 60 MPa conditions using, for example, Spark Plasma Sintering (SPS) equipment, or 400 to 400 using a hot-press equipment. It may proceed for 1 to 60 minutes at 550 °C, 180 to 250MPa conditions.
  • SPS Spark Plasma Sintering
  • thermoelectric leg powder may be sintered together with the amorphous ribbon.
  • the powder for thermoelectric legs is sintered together with the amorphous ribbon, the electrical conductivity becomes high, so that high thermoelectric performance can be obtained.
  • the amorphous ribbon may be an Fe-based amorphous ribbon.
  • the amorphous ribbon may be sintered after the thermoelectric legs are disposed on the side for bonding with the upper electrode and the side for bonding with the lower electrode. Accordingly, electrical conductivity may be increased in the direction of the upper electrode or the lower electrode.
  • the lower amorphous ribbon, the powder for thermoelectric legs and the upper amorphous ribbon can be sequentially placed in the mold and then sintered.
  • a surface treatment layer may be formed on the lower amorphous ribbon and the upper amorphous ribbon, respectively.
  • the surface treatment layer is a thin film formed by a plating method, a sputtering method, a vapor deposition method, or the like. Nickel or the like having little change in performance even when reacted with a thermoelectric leg powder as a semiconductor material may be used.
  • the amorphous ribbon may be disposed on the side of the thermoelectric leg and then sintered. Accordingly, electrical conductivity may be increased along the side of the thermoelectric leg.
  • the thermoelectric leg powder can be filled and sintered.
  • thermoelectric device may act on a power generation device, a cooling device, a heating device, and the like.
  • the thermoelectric device according to the embodiment of the present invention mainly includes optical communication modules, sensors, medical devices, measuring devices, aerospace industry, refrigerators, chillers, automobile ventilation sheets, cup holders, washing machines, dryers, and wine cellars. It can be applied to water purifier, sensor power supply, thermopile and the like.
  • PCR equipment is a device for amplifying DNA to determine the DNA sequence, precise temperature control is required, and a thermal cycle (thermal cycle) equipment is required.
  • a Peltier-based thermoelectric device may be applied.
  • thermoelectric device Another example in which a thermoelectric device according to an embodiment of the present invention is applied to a medical device is a photo detector.
  • the photo detector includes an infrared / ultraviolet detector, a charge coupled device (CCD) sensor, an X-ray detector, a thermoelectric thermal reference source (TTRS), and the like.
  • Peltier-based thermoelectric elements may be applied for cooling the photo detector. As a result, it is possible to prevent a change in wavelength, a decrease in power, a decrease in resolution, etc. due to a temperature rise inside the photodetector.
  • thermoelectric device As another example in which the thermoelectric device according to an embodiment of the present invention is applied to a medical device, the field of immunoassay, in vitro diagnostics, general temperature control and cooling systems, Physiotherapy, liquid chiller systems, blood / plasma temperature control. Thus, precise temperature control is possible.
  • thermoelectric device according to an embodiment of the present invention is applied to a medical device.
  • a medical device is an artificial heart.
  • power can be supplied to the artificial heart.
  • thermoelectric device examples include a star tracking system, a thermal imaging camera, an infrared / ultraviolet detector, a CCD sensor, a hubble space telescope, and a TTRS. Accordingly, the temperature of the image sensor can be maintained.
  • thermoelectric device according to the embodiment of the present invention is applied to the aerospace industry includes a cooling device, a heater, a power generation device, and the like.
  • thermoelectric device according to the embodiment of the present invention may be applied for power generation, cooling, and heating in other industrial fields.

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  • Cooling Or The Like Of Semiconductors Or Solid State Devices (AREA)
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JP2019540635A JP7293116B2 (ja) 2017-02-06 2018-02-06 熱電焼結体および熱電素子
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