Thermoelectric element including diffusion barrier layer and home appliance including same

Abstract

A thermoelectric element according to an embodiment of the present disclosure may include: a Bi-Te-based thermoelectric leg; a first diffusion barrier layer disposed above and / or below the thermoelectric leg and comprising multi-layers including a plurality of stacked alloy layers (131), each stacked alloy layer (131) having a thickness of 1-30 nm and including a nickel (Ni)-chromium (Cr) alloy or a nickel (Ni)-vanadium (V) alloy; and a second diffusion barrier layer disposed on one side of the first diffusion barrier layer and including gold (Au), silver (Ag), tin (Sn), or a combination thereof.

Description

Thermoelectric element including a diffusion barrier layer and home appliance including the same

[0001] One embodiment disclosed in this document relates to a thermoelectric element including a diffusion barrier layer and a home appliance including the same.

[0002] In general, thermoelectric devices are referred to by various names such as thermoelectric modules, Peltier elements, thermoelectric coolers (TECs), or thermoelectric modules (TEMs). Thermoelectric devices consist of N-type and P-type thermoelectric materials (thermoelectric legs) and electrodes such as nickel (Ni) and cobalt (Co). Thermoelectric devices may include a diffusion barrier layer, which is mainly placed between the thermoelectric semiconductor device and the electrode to limit mutual diffusion between the thermoelectric material and the electrode.

[0003] When a direct current (DC) voltage is applied to both ends of a thermoelectric element, heat moves from the heat-absorbing part to the heat-generating part according to the flow of electrons in N-type thermoelectric materials and according to the flow of holes in P-type thermoelectric materials. In some cases, if the polarity of the applied voltage is changed, the positions of the heat-absorbing part and the heat-generating part are reversed, and the heat flow is also reversed. Through this principle, the thermoelectric element can serve as a heat pump that absorbs heat from a low-temperature heat source and supplies it to a high-temperature heat source, or as a thermoelectric generator (TEG) that generates an electromotive force by moving electrons and holes inside the thermoelectric element due to the temperature difference between the two ends.

[0004] A thermoelectric element according to one embodiment of the present disclosure may include a Bi-Te-based thermoelectric leg, a first diffusion prevention layer comprising a plurality of stacked alloy layers (131) disposed on the upper and / or lower side of the thermoelectric leg, wherein each of the stacked alloy layers (131) has a thickness of 1 nm to 30 nm and comprises a first diffusion prevention layer comprising a nickel (Ni)-chromium (Cr) alloy or a nickel (Ni)-vanadium (V) alloy, and a second diffusion prevention layer disposed on one side of the first diffusion prevention layer comprising gold (Au), silver (Ag), tin (Sn), or a combination thereof.

[0005] A refrigerator according to one embodiment of the present disclosure may include a main body, a door rotatably connected to open and close the main body, a storage room disposed inside the main body for storing food, and a cold air supply device configured to supply cold air to the storage room and including a thermoelectric element. The thermoelectric element may include a Bi-Te-based thermoelectric leg, a first diffusion prevention layer disposed on the upper and / or lower side of the thermoelectric leg and comprising a plurality of stacked alloy layers (131), wherein each of the stacked alloy layers (131) may comprise a first diffusion prevention layer comprising a nickel (Ni)-chromium (Cr) alloy or a nickel (Ni)-vanadium (V) alloy, and a first diffusion prevention layer disposed on one side of the first diffusion prevention layer and may include gold (Au), silver (Ag), tin (Sn), or a combination thereof.

[0006] A method for manufacturing a thermoelectric element according to one embodiment of the present disclosure, comprising a Bi-Te-based thermoelectric leg (110), a first diffusion prevention layer (130a) on one side of the thermoelectric leg comprising a plurality of stacked alloy layers (131), wherein each of the stacked alloy layers (131) comprises a first diffusion prevention layer (130a) comprising a nickel (Ni)-chromium (Cr) alloy or a nickel (Ni)-vanadium (V) alloy, and a second diffusion prevention layer (130b) disposed on one side of the first diffusion prevention layer comprising gold (Au), silver (Ag), tin (Sn), or a combination thereof, may include a plasma cleaning process of the thermoelectric leg, a process of depositing a first diffusion prevention layer on the thermoelectric leg through a first sputtering unit, and a process of depositing a second diffusion prevention layer on the first diffusion prevention layer through a second sputtering unit.

[0007] However, the problems to be solved in this disclosure are not limited to those mentioned above, and may be determined in various ways without departing from the spirit and scope of this disclosure.

[0008] FIG. 1 is a perspective view showing a thermoelectric element having stacked diffusion prevention layers according to one embodiment of the present disclosure.

[0009] FIG. 2 is a cross-sectional view and an enlarged view of some layers of a thermoelectric element having a plurality of layers stacked according to one embodiment of the present disclosure.

[0010] FIG. 3 is a cross-sectional view and an enlarged view of some layers of a thermoelectric element having a plurality of layers stacked according to one embodiment of the present disclosure.

[0011] FIG. 4 is a cross-sectional view taken through equipment of a portion of a thermoelectric element having a plurality of layers stacked according to one embodiment of the present disclosure.

[0012] FIG. 5 is a cross-sectional view taken through equipment of a thermoelectric element having a plurality of layers stacked according to one embodiment of the present disclosure.

[0013] FIGS. 6a and 6b are flowcharts illustrating a manufacturing process of a thermoelectric element according to one embodiment of the present disclosure.

[0014] FIGS. 7A, 7B, 7C, and 7D are drawings showing equipment for depositing a multilayer diffusion barrier layer during a manufacturing process of a thermoelectric element according to one embodiment of the present disclosure.

[0015] FIG. 8 is a graph showing the results of an adhesion strength test between a diffusion prevention layer composed of a single layer and a diffusion prevention layer composed of multiple layers, according to one embodiment of the present disclosure.

[0016] FIG. 9 is a diagram showing a comparative experiment related to the thickness of the first diffusion barrier layer of a thermoelectric element according to one embodiment of the present disclosure.

[0017] FIG. 10 is a perspective view of a refrigerator according to one embodiment of the present disclosure.

[0018] The various embodiments of this document and the terms used therein are not intended to limit the technical features described in this document to specific embodiments, and should be understood to include various modifications, equivalents, or substitutions of said embodiments.

[0019] In relation to the description of the drawings, similar reference numerals may be used for similar or related components.

[0020] The singular form of the noun corresponding to the item may include one or multiple items, unless the relevant context clearly indicates otherwise.

[0021] In this document, each of the phrases such as "A or B", "at least one of A and B", "at least one of A or B", "A, B or C", "at least one of A, B and C", and "at least one of A, B, or C" may include any one of the items listed together in the corresponding phrase, or all possible combinations thereof.

[0022] In this document, the term “and / or” includes a combination of multiple related described components or any of the multiple related described components.

[0023] In this document, terms such as "first," "second," or "first" or "second" may be used simply to distinguish a component from another component and do not limit the components in any other aspect (e.g., importance or order).

[0024] In this document, terms such as "front," "rear," "top," "bottom," "side," "left," "right," "top," and "bottom" are defined based on the drawings, and the shape and location of each component are not limited by these terms.

[0025] Where any (e.g., 1st) component is referred to as "coupled" or "connected" to another (e.g., 2nd) component, with or without the terms "functionally" or "communicationly," it means that said any component may be connected to said other component directly (e.g., via a wire), wirelessly, or through a third component.

[0026] Terms such as "include" or "have" are intended to specify the existence of the features, numbers, steps, actions, components, parts, or combinations thereof described in this document, and do not preclude the existence or addition of one or more other features, numbers, steps, actions, components, parts, or combinations thereof.

[0027] When it is said that a component is "connected," "combined," "supported," or "in contact" with another component, this includes not only cases where the components are directly connected, combined, supported, or in contact, but also cases where they are indirectly connected, combined, supported, or in contact through a third component.

[0028] When it is said that a component is located "on" another component, this includes not only cases where one component is in contact with the other, but also cases where another component exists between the two components.

[0029] A refrigerator according to one embodiment may include a main body.

[0030] The "main body" may include an inner body, an outer body positioned on the outside of the inner body, and an insulating material provided between the inner body and the outer body.

[0031] The "inner body" may include at least one of a case, plate, panel, or liner forming a storage chamber. The inner body may be formed as a single body or may be formed by assembling multiple plates. The "outer body" may form the exterior of the main body and may be coupled to the outer side of the inner body so that an insulating material is disposed between the inner body and the outer body.

[0032] The "insulating material" can insulate the interior and exterior of the storage room so that the temperature inside the storage room is maintained at a set appropriate temperature without being affected by the external environment. According to one embodiment, the insulating material may include a foamed insulating material. The foamed insulating material can be formed by injecting and foaming urethane foam, which is a mixture of polyurethane and a foaming agent, between the inner and outer layers.

[0033] According to one embodiment, the insulation material may additionally include a vacuum insulation material in addition to a foam insulation material, or the insulation material may consist solely of a vacuum insulation material instead of a foam insulation material. The vacuum insulation material may include a core material and an outer shell material that accommodates the core material and seals the interior under vacuum or near-vacuum pressure. However, the insulation material is not limited to the foam insulation material or vacuum insulation material described above and may include various materials that can be used for insulation.

[0034] The "storage room" may include a space defined by an internal structure. The storage room may further include an internal structure defining a space corresponding to the storage room. Various items such as food, medicine, and cosmetics may be stored in the storage room, and the storage room may be formed so that at least one side is open to allow for the retrieval and retrieval of items.

[0035] A refrigerator may include one or more storage compartments. When two or more storage compartments are formed in a refrigerator, each storage compartment may have a different use and may be maintained at a different temperature. To this end, each storage compartment may be partitioned from one another by a partition containing insulation.

[0036] The storage room may be provided to be maintained within an appropriate temperature range according to its intended use and may include a "refrigeration room," "freezing room," or "variable temperature room" distinguished according to its intended use and / or temperature range. The refrigerator room may be maintained at a temperature suitable for refrigerated storage of goods, and the freezer room may be maintained at a temperature suitable for frozen storage of goods. "Refrigeration" may mean cooling goods to a temperature that does not freeze them; for example, the refrigerator room may be maintained within a range of 0 degrees Celsius to 7 degrees Celsius. "Freezing" may mean cooling goods to freeze them or to maintain them in a frozen state; for example, the freezer room may be maintained within a range of -20 degrees Celsius to -1 degree Celsius. The variable temperature room may be used as either a refrigerator room or a freezer room, with or without the user's choice.

[0037] Storage rooms may be referred to by various names, such as "vegetable room," "fresh room," "cooling room," and "ice-making room," in addition to terms like "refrigeration room," "freezing room," and "variable temperature room." The terms "refrigeration room," "freezing room," and "variable temperature room" used below should be understood as encompassing storage rooms with corresponding uses and temperature ranges.

[0038] According to one embodiment, the refrigerator may include at least one door configured to open and close one side of the storage compartment. The door may be configured to open and close each of one or more storage compartments, or a single door may be configured to open and close multiple storage compartments. The door may be installed to be rotatable or sliding on the front of the main body.

[0039] The “door” may be configured to seal the storage room when the door is closed. The door may include insulation material, similar to the main body, to insulate the storage room when the door is closed.

[0040] According to one embodiment, the door may include a door outer panel forming the front of the door, a door inner panel forming the rear of the door and facing the storage room, an upper cap, a lower cap, and a door insulation material provided inside them.

[0041] A gasket may be provided on the edge of the door inner panel to seal the storage compartment by adhering to the front of the main body when the door is closed. The door inner panel may include a dyke that protrudes rearward to allow a door basket for storing items to be mounted.

[0042] According to one embodiment, the door may include a door body and a front panel detachably coupled to the front side of the door body and forming the front of the door. The door body may include a door outer panel forming the front of the door body, a door inner panel forming the rear of the door body and facing the storage compartment, an upper cap, a lower cap, and a door insulation material provided inside them.

[0043] Refrigerators can be classified into French Door Type, Side-by-side Type, BMF (Bottom Mounted Freezer), TMF (Top Mounted Freezer), or 1-door refrigerators depending on the arrangement of the door and storage compartment.

[0044] According to one embodiment, the refrigerator may include a cold air supply device arranged to supply cold air to the storage compartment.

[0045] The "cold air supply device" may include a machine, apparatus, electronic device, and / or a system combining these that can generate cold air and guide cold air to cool a storage room.

[0046] According to one embodiment, a cold air supply device can generate cold air through a refrigeration cycle that includes the processes of compression, condensation, expansion, and evaporation of a refrigerant. To this end, the cold air supply device may include a refrigeration cycle device having a compressor, a condenser, an expansion device, and an evaporator capable of driving the refrigeration cycle. According to one embodiment, the cold air supply device may include a semiconductor such as a thermoelectric element. The thermoelectric element can cool a storage chamber through heat generation and cooling action via the Peltier effect.

[0047] According to one embodiment, the refrigerator may include a machine room arranged to accommodate at least some parts belonging to a cold air supply device.

[0048] The "machine room" may be configured to be partitioned and insulated from the storage room to prevent heat generated from components placed in the machine room from being transferred to the storage room. The interior of the machine room may be configured to communicate with the exterior of the main body to dissipate heat from components placed inside the machine room.

[0049] According to one embodiment, the refrigerator may include a dispenser provided on the door to provide water and / or ice. The dispenser may be provided on the door so that it is accessible to a user without opening the door.

[0050] According to one embodiment, the refrigerator may include an ice-making device configured to generate ice. The ice-making device may include an ice-making tray that stores water, an ice-removing device that separates ice from the ice-making tray, and an ice bucket that stores the ice generated from the ice-making tray.

[0051] According to one embodiment, the refrigerator may include a control unit for controlling the refrigerator.

[0052] The "control unit" may include a memory that stores or remembers a program and / or data for controlling a refrigerator, and a processor that outputs a control signal for controlling a cold air supply device, etc., according to the program and / or data stored in the memory.

[0053] The memory stores or records various information, data, commands, programs, etc., necessary for the operation of the refrigerator. The memory can store temporary data generated while generating control signals to control the components included in the refrigerator. The memory may include at least one of volatile memory or non-volatile memory, or a combination thereof.

[0054] The processor controls the overall operation of the refrigerator. The processor can control the refrigerator's components by executing programs stored in memory. The processor may include a separate NPU that performs the operation of an artificial intelligence model. Additionally, the processor may include a central processing unit, a graphics-only processor (GPU), etc. The processor can generate control signals to control the operation of the cold air supply unit. For example, the processor may receive temperature information of the storage compartment from a temperature sensor and generate a cooling control signal to control the operation of the cold air supply unit based on the temperature information of the storage compartment.

[0055] Additionally, the processor can process user input of the user interface and control the operation of the user interface according to programs and / or data stored in memory. The user interface may be provided using an input interface and an output interface. The processor can receive user input from the user interface. Additionally, the processor can transmit display control signals and image data to the user interface to display an image on the user interface in response to the user input.

[0056] The processor and memory may be provided as a single unit or separately. The processor may include one or more processors. For example, the processor may include a main processor and at least one sub-processor. The memory may include one or more memory units.

[0057] According to one embodiment, the refrigerator may include a processor and memory that control all components included in the refrigerator, and may include a plurality of processors and a plurality of memories that individually control the components of the refrigerator. For example, the refrigerator may include a processor and memory that control the operation of a cold air supply device according to the output of a temperature sensor. Additionally, the refrigerator may separately provide a processor and memory that control the operation of a user interface according to user input.

[0058] The communication module can communicate with external devices, such as servers, mobile devices, and other home appliances, through nearby Access Points (APs). The Access Point (AP) can connect the Local Area Network (LAN) to which the refrigerator or user device is connected to the Wide Area Network (WAN) to which the server is connected. The refrigerator or user device can be connected to the server through the Wide Area Network (WAN).

[0059] The input interface may include keys, touchscreens, microphones, etc. The input interface may receive user input and transmit it to the processor.

[0060] The output interface may include a display, a speaker, etc. The output interface can output various notifications, messages, information, etc. generated by the processor.

[0061] Hereinafter, embodiments according to the present invention will be described in detail with reference to the attached drawings.

[0062] Meanwhile, terms such as "upward," "downward," "front," and "rear" used in the following description are defined based on the drawings, and the shape and location of each component are not limited by these terms. For example, the terms "front" and "rear" below may refer to the front and rear of the refrigerator in the X-direction, respectively, based on the drawings. The terms "upward" and "downward" below may refer to the upward and downward directions of the refrigerator in the Z-direction, respectively, based on the drawings. The terms "left" and "right" below may refer to the left and right directions of the refrigerator in the Y-direction, respectively, based on the drawings.

[0063] Hereinafter, a thermoelectric semiconductor (hereinafter referred to as a thermoelectric element) used in a cold air supply device will be described. The thermoelectric element is described as a semiconductor for cooling the storage compartment of a refrigerator, but is not limited thereto and can be easily modified in design and applied to various home appliances where thermoelectric elements are utilized, such as air purifiers, robot vacuum cleaners, cooking appliances, or washing machines.

[0064] FIG. 1 is a perspective view showing a thermoelectric element having stacked diffusion prevention layers according to one embodiment of the present disclosure.

[0065] Referring to FIG. 1, the thermoelectric element (100) may include a thermoelectric leg (110) (e.g., thermoelectric material) having at least one diffusion barrier layer (130) stacked thereon. The at least one diffusion barrier layer (130) may be formed on the thermoelectric leg (110) by a dry deposition process.

[0066] According to one embodiment, the thermoelectric element (100) may include a first substrate (300a), a second substrate (300b) disposed parallel to the first substrate (300a), a first electrode (200a) disposed on the first substrate (300a), a second electrode (200b) disposed on the second substrate (300b), and a thermoelectric leg (110) disposed between the first electrode (200a) and the second electrode (200b). The first electrode (200a) and the second electrode (200b) may be disposed between the first substrate (300a) and the second substrate (300b). The first electrode (200a) and the second electrode (200b) may form a designated pattern and may be arranged in a plurality.

[0067] According to one embodiment, the first substrate (300a) and the second substrate (300b) can each generate an exothermic or endothermic reaction when power is applied to the thermoelectric element (100). The first substrate (300a) and the second substrate (300b) can each be formed in the shape of a plate and made of various materials. According to one embodiment, the first substrate (300a) and / or the second substrate (300b) can be formed of a non-conductive material such as ceramic or an insulating resin. For example, the first substrate (300a) and / or the second substrate (300b) may be at least one of Al2O3, AlN, SiC, or ZrO2, or a combination thereof. According to one embodiment, the first substrate (300a) and / or the second substrate (300b) may be substrates of a conductive material capable of conducting electricity (e.g., metal). For example, the first substrate (300a) and / or the second substrate (300b) may be one or a combination of aluminum (Al), zinc (Zn), copper (Cu), nickel (Ni), or cobalt (Co). If the first substrate (300a) and / or the second substrate (300b) are made of a conductive material, an insulating layer may be disposed between the substrate (300a, 300b) and the electrode (200a, 200b) so as not to be electrically connected to the electrode (200a, 200b).

[0068] According to one embodiment, a first substrate (300a) and a second substrate (300b) are arranged to face each other, and a plurality of first electrodes (200a) may be arranged on the inner surface of the first substrate (300a), and a plurality of second electrodes (200b) may be arranged on the inner surface of the second substrate (300b). At least a portion of the first electrodes (200a) and the second electrodes (200b) may be arranged to face each other and may be formed of a conductive material (e.g., a metal material) through which current can travel. For example, the first electrode (200a) and / or the second electrode (200b) may be one or a combination of aluminum (Al), zinc (Zn), copper (Cu), cobalt (Co), nickel (Ni), gold (Au), silver (Ag), copper (Cu), and titanium (Ti). The first electrode (200a) and the second electrode (200b) may be formed of the same material or different material.

[0069] According to one embodiment, the first electrode (200a) and / or the second electrode (200b) may form a pattern of a specified shape. For example, a plurality of first electrodes (200a) may be arranged at specified intervals on the first substrate (300a). For example, a plurality of second electrodes (200b) may be arranged at specified intervals on the second substrate (300b). The arrangement of the plurality of first electrodes (200a) and the plurality of second electrodes (200b) is not limited to the pattern disclosed in FIG. 1 and may be modified to various patterns that can easily transmit current.

[0070] According to one embodiment, a plurality of thermoelectric legs (110) may each be disposed between a first electrode (200a) and a second electrode (200b). Each thermoelectric leg (110) may have one side connected to the first electrode (200a) and the other side connected to the second electrode (200b). The thermoelectric leg (110) includes a plurality of P-type thermoelectric legs (110a) and a plurality of N-type thermoelectric legs (110b), and the P-type thermoelectric legs (110) and N-type thermoelectric legs (110) may be arranged alternately in one direction.

[0071] According to one embodiment, adjacent P-type thermoelectric legs (110a) in one direction may have their upper and lower surfaces electrically connected in series with the first electrode (200a) and the second electrode (200b). According to one embodiment, adjacent N-type thermoelectric legs (110) in one direction may have their upper and lower surfaces electrically connected in series with the first electrode (200a) and the second electrode (200b).

[0072] According to one embodiment, a thermoelectric leg (110) (e.g., P-type thermoelectric legs (110a) and N-type thermoelectric legs (110)) may include a diffusion prevention layer (130). The diffusion prevention layer (130) may include a first diffusion prevention layer (e.g., the first diffusion prevention layer (130a) of FIG. 2) disposed on the upper and / or lower side of the thermoelectric leg (110) and a second diffusion prevention layer (e.g., the second diffusion prevention layer (130b) of FIG. 2) disposed on one side of the first diffusion prevention layer (130a). The first diffusion prevention layer (130a) and the second diffusion prevention layer (130b) may be composed of different materials.

[0073] According to one embodiment, the first electrode (200a) and the second electrode (200b) of the thermoelectric element (100) can be electrically connected to a power source. When an external DC voltage is applied, the holes of the P-type thermoelectric leg (110a) and the electrons of the N-type thermoelectric leg (110b) move, thereby causing heat generation and heat absorption to occur at both ends of the thermoelectric leg (110).

[0074] According to one embodiment, at least one of the first electrode (200a) and the second electrode (200b) of the thermoelectric element (100) may be exposed to a heat source. When heat is supplied by an external heat source, electrons and holes move, causing a flow of current in the thermoelectric element to generate electricity.

[0075] Below, the diffusion prevention layer (130) of the thermoelectric element (100) will be described in detail.

[0076] FIG. 2 is a cross-sectional view and an enlarged view of some layers of a thermoelectric element having a plurality of layers stacked according to one embodiment of the present disclosure.

[0077] FIG. 3 is a cross-sectional view and an enlarged view of some layers of a thermoelectric element having a plurality of layers stacked according to one embodiment of the present disclosure.

[0078] FIG. 4 is a cross-sectional view taken through equipment of a portion of a thermoelectric element having a plurality of layers stacked according to one embodiment of the present disclosure.

[0079] FIG. 5 is a cross-sectional view taken through equipment of a thermoelectric element having a plurality of layers stacked according to one embodiment of the present disclosure.

[0080] Referring to FIGS. 2 to 5, the thermoelectric element (100) may include a thermoelectric leg (110) (e.g., a Peltier leg) and a diffusion prevention layer (130). The diffusion prevention layer (130) may include a first diffusion prevention layer (130a) and a second diffusion prevention layer (130b). The configuration of the thermoelectric element (100) of FIGS. 2 to 5 may be partially or entirely identical to the configuration of the thermoelectric element (100) of FIG. 1.

[0081] The embodiments of FIGS. 2 to 5 can be optionally combined with the embodiments of FIGS. 1 and FIGS. 6a to 10.

[0082] According to one embodiment, the thermoelectric element (100) may include a thermoelectric leg (110) and a first diffusion prevention layer (130a) disposed on the upper and / or lower side of the thermoelectric leg (110). According to one embodiment, the thermoelectric element (100) may include a thermoelectric leg (110), a first diffusion prevention layer (130a) disposed on the upper and / or lower side of the thermoelectric leg (110), and a second diffusion prevention layer (130b) disposed on one side of the first diffusion prevention layer (130a).

[0083] According to one embodiment, the thermoelectric leg (110) of the thermoelectric element (100) may be a thermoelectric semiconductor, a thermoelectric material in which a temperature difference occurs between two ends when electricity is applied, or a thermoelectric material in which electricity is generated by the temperature difference between two ends. The thermoelectric leg (110) may be designed in a cylindrical shape. The thermoelectric leg (110) may be a P-type thermoelectric leg (110a) of FIG. 1 or an N-type thermoelectric leg (110).

[0084] According to one embodiment, the material of the thermoelectric leg (110) may include at least one element selected from the group consisting of transition metals, rare earth elements, group 13 elements, group 14 elements, group 15 elements, or group 16 elements. For example, the rare earth elements may include elements such as Y, Ce, and La, the transition metal may be one of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Zn, Ag, or Re, examples of the group 13 elements may be one of B, Al, Ga, or In, examples of the group 14 elements may be one of C, Si, Ge, Sn, or Pb, examples of the group 15 elements may be one of P, As, Sb, or Bi, and examples of the group 16 elements may be one of S, Se, or Te.

[0085] According to one embodiment, the thermoelectric leg (110) may be composed of a composition including at least two of bismuth (Bi), tellurium (Te), cobalt (Co), samarium (Sm), antimony (Sb), indium (In), or cerium (Ce). For example, the thermoelectric leg (110) may be at least one of a Bi-Te system, a Co-Sb system, a Pb-Te system, a Ge-Te system, a Si-Ge system, a Sb-Te system, a Sm-Co system, a transition metal silicide system, a skuttrudite system, a silicide system, or a Half-heusler system. For example, the thermoelectric leg (110) may include a (Bi,Sb)2(Te,Se)3 system thermoelectric semiconductor in which Sb and Se are used as dopants as a Bi-Te system thermoelectric semiconductor. For example, the thermoelectric leg (110) may include a CoSb3-based thermoelectric semiconductor as a Co-Sb-based thermoelectric semiconductor. For example, the thermoelectric leg (110) may include AgSbTe2 or CuSbTe2 as an Sb-Te-based thermoelectric semiconductor. For example, the thermoelectric leg (110) may include PbTe or (PbTe)mAgSbTe2 as a Pb-Te-based thermoelectric semiconductor. Hereinafter, the thermoelectric leg (110) is described on the premise that it is composed of a Bi-Te-based thermoelectric material.

[0086] According to one embodiment, the first diffusion prevention layer (130a) may be disposed on the upper and / or lower side of the thermoelectric leg (110).

[0087] According to one embodiment, the first diffusion prevention layer (130a) may be optionally disposed on the upper or lower side of the thermoelectric leg (110). For example, the thermoelectric leg (110) may include a first surface (111) facing a first direction (e.g., +Z-axis direction) and a second surface (112) facing a second direction (e.g., -Z-axis direction) opposite to the first direction (e.g., +Z-axis direction). For example, the first diffusion prevention layer (130a) may be disposed on the first surface (111) of the thermoelectric leg (110). The first diffusion prevention layer (130a) may be deposited on the first surface (111) of the thermoelectric leg (110). For example, the first diffusion prevention layer (130a) may be disposed on the second surface (112) of the thermoelectric leg (110). The first diffusion prevention layer (130a) can be deposited on the second surface (112) of the thermoelectric leg (110).

[0088] According to one embodiment, the first diffusion prevention layer (130a) may be arranged side by side on the upper and lower sides of the thermoelectric leg (110). For example, when the first diffusion prevention layer (130a) is placed on the upper and lower sides of the thermoelectric leg (110), the first diffusion prevention layer (130a) may include a first-1 diffusion prevention layer (130aa) placed on the upper side (e.g., the first surface (111)) of the thermoelectric leg (110), and a first-2 diffusion prevention layer (130ab) placed on the lower side (e.g., the second surface (112)) of the thermoelectric leg (110). The first-1 diffusion prevention layer (130aa) and the first-2 diffusion prevention layer (130ab) may be formed with corresponding thicknesses and materials.

[0089] According to one embodiment, the first diffusion barrier layer (130a) may include one or more metal powders selected from the group consisting of chromium (Cr), nickel (Ni), platinum (Pt), titanium (Ti), tungsten (W), silicon (Si), manganese (Mn), iron (Fe), cobalt (Co), copper (Cu), or molybdenum (Mo) and alloys thereof. However, the material of the first diffusion barrier layer (130a) is not limited to the aforementioned materials and can be varied to a metal or heavy metal with a melting point exceeding 1,000°C.

[0090] According to one embodiment, the first diffusion barrier layer (130a) may be a Ni-X alloy, wherein X may be at least one of Cr, V, Al, Co, W, Sn, Zn, or Pb. According to one embodiment, the first diffusion barrier layer (130a) may include a nickel (Ni)-chromium (Cr) alloy or a nickel (Ni)-vanadium (V) alloy. For example, the first diffusion barrier layer (130a) may form a structure in which a plurality of nickel (Ni)-chromium (Cr) alloy layers are stacked (e.g., a multilayer structure). For example, the first diffusion barrier layer (130a) may form a structure in which a plurality of nickel (Ni)-vanadium (V) alloy layers are stacked (e.g., a multilayer structure).

[0091] According to one embodiment, the first diffusion barrier layer (130a) may be a Ni-X alloy, and the content of X may be relatively small compared to the content of Ni. According to one embodiment, in the first diffusion barrier layer (130a) formed from a nickel (Ni)-chromium (Cr) alloy, the alloy amount of chromium (Cr) may be 20 ± 10 wt% relative to the total weight. For example, in the first diffusion barrier layer (130a), the alloy amount of chromium (Cr) may be approximately 20 wt% relative to the total weight. According to one embodiment, in the first diffusion barrier layer (130a) formed from a nickel (Ni)-vanadium (V) alloy, the alloy amount of vanadium (V) may be 10 ± 5 wt% relative to the total weight. For example, in the first diffusion barrier layer (130a), the alloy amount of vanadium (V) may be approximately 7 wt% relative to the total weight.

[0092] According to one embodiment, the first diffusion barrier layer (130a) may be composed of a multi-layer in which a plurality of first alloy layers (131) are stacked. The first alloy layer (131) may include the aforementioned nickel (Ni)-chromium (Cr) alloy or nickel (Ni)-vanadium (V) alloy. Each of the first alloy layers (131) forming the multi-layer may have a thickness of approximately 30 nm or less. For example, each of the first alloy layers (131) may have a thickness of approximately 1.0 nm to 30.0 nm. For example, each of the first alloy layers (131) may have a thickness of approximately 2.0 nm to 30.0 nm. For example, each of the first alloy layers (131) may have a thickness of approximately 13.0 nm to 15.0 nm.

[0093] According to one embodiment, the first diffusion prevention layer (130a) comprises a plurality of first alloy layers (131) stacked therein, and the total thickness of the first diffusion prevention layer (130a) may be the sum of the thicknesses of the first alloy layers (131). According to one embodiment, the total thickness of the first diffusion prevention layer (130a) may be greater than the total thickness of the second diffusion prevention layer (130b). According to one embodiment, the total thickness of the first diffusion prevention layer (130a) may be smaller than the thickness of the thermoelectric leg (110). The thickness of the first diffusion prevention layer (130a) may be approximately 10.0 μm or less. For example, the thickness of the first diffusion prevention layer (130a) may be approximately 1.0 μm to 10.0 μm. For example, the thickness of the first diffusion prevention layer (130a) may be approximately 3.0 μm to 5.0 μm.

[0094] According to one embodiment, the first diffusion prevention layer (130a) has a structure in which a plurality of first alloy layers (131) are stacked, and can be stacked on the thermoelectric leg (110) by a dry deposition process. For example, the first diffusion prevention layer (130a) may have a structure in which approximately 100 to 1000 first alloy layers (131) are stacked. For example, the first diffusion prevention layer (130a) may have a structure in which approximately 200 to 400 first alloy layers (131) are stacked.

[0095] According to one embodiment, the first diffusion barrier layer (130a) can minimize internal stress by depositing each of the first alloy layers (131) on the upper and / or lower side of the thermoelectric leg (110) by a dry deposition process. Generally, when directly soldering tin (Sn) to a thermoelectric leg (e.g., Bi-Te-based thermoelectric material), Sn-Te-based intermetallic compounds (IMCs) are formed by thermal diffusion, which can cause brittleness and frequently lead to the failure of the thermoelectric element. The thermoelectric element (100) of the present disclosure can minimize internal stress of the thermoelectric element (100) by proceeding with a sputtering process when depositing the first alloy layers (131) on the thermoelectric leg (110), and by forming a multilayer that provides a cooling time for a specified interval after one first alloy layer (131) is deposited. The above-mentioned internal stress minimization can improve the long-term durability of the thermoelectric element (100) by increasing the adhesion strength between the thermoelectric leg (110) and the first diffusion prevention layer (130a).

[0096] According to one embodiment, the first diffusion barrier layer (130a) may be formed as a multi-layer in which a plurality of first alloy layers (131) are stacked. When the first alloy layers (131) are deposited on the thermoelectric leg (110), a cooling time is provided after the sputtering process, so that an interlayer interface (132) that is easy to distinguish between adjacent first alloy layers (131) may be formed.

[0097] Referring to FIG. 4, an enlarged view of the first diffusion barrier layer (130a) can be seen through analysis equipment. The analysis equipment used is a transmission electron microscope (TEM), which can analyze the internal structure of a material at high resolution using an electron beam. Referring to FIG. 4, the first diffusion barrier layer (130a) deposited on the thermoelectric leg (110) is shown, and in an enlarged view of a portion (S) of the first diffusion barrier layer (130a), it can be seen that the first diffusion barrier layer (130a) forms a multi-layer. For example, the first alloy layers (131) may be distinguishable from adjacent first alloy layers (131) by forming an interlayer interface (132). The interlayer interface (132) is a process in which the surface of the first alloy layer (131) comes into contact with external air due to a cooling time provided at specified intervals during the sputtering process, and appears as a color distinct from the inner side of the first alloy layer (131) by TEM imaging. The first diffusion barrier layer (130a) shown in FIG. 4 is a nickel (Ni)-chromium (Cr) alloy layer (or nickel (Ni)-vanadium (V) alloy layer), and the thickness of each alloy layer was confirmed to be approximately 13.0 nm to 15.0 nm.

[0098] According to one embodiment, the second diffusion prevention layer (130b) may be disposed on one side (e.g., the upper or lower side) of the first diffusion prevention layer (130a).

[0099] According to one embodiment, a first diffusion prevention layer (130a) (e.g., a first-1 diffusion prevention layer (130aa)) disposed on the upper side of a thermoelectric leg (110) may include a first surface facing a first direction (e.g., +Z axis direction) and a second surface facing a second direction (e.g., -Z axis direction) opposite to the first direction (e.g., +Z axis direction) (e.g., a surface facing the -Z axis). A second diffusion prevention layer (130b) may be disposed on the first surface of the first-1 diffusion prevention layer (130aa). The second diffusion prevention layer (130b) may be deposited on the first surface of the first-1 diffusion prevention layer (130aa).

[0100] According to one embodiment, a first diffusion prevention layer (130a) (e.g., a first-second diffusion prevention layer (130ab)) disposed on the lower side of a thermoelectric leg (110) may include a first surface facing a first direction (e.g., +Z-axis direction) and a second surface facing a second direction (e.g., -Z-axis direction) opposite to the first direction (e.g., +Z-axis direction). A second diffusion prevention layer (130b) may be disposed on the second surface of the first-second diffusion prevention layer (130ab). The second diffusion prevention layer (130b) may be deposited on the second surface of the first-second diffusion prevention layer (130ab).

[0101] According to one embodiment, the first diffusion prevention layer (130a) may be arranged side by side on the upper and lower sides of the thermoelectric leg (110). The second diffusion prevention layer (130b) may be disposed on a pair of first diffusion prevention layers (130a) arranged on the upper and lower sides of the thermoelectric leg (110). For example, the second diffusion prevention layer (130b) may include a second-1 diffusion prevention layer (130ba) disposed on a first-1 diffusion prevention layer (130aa) disposed on the upper side of the thermoelectric leg (110), and a second-2 diffusion prevention layer (130bb) disposed on a first-2 diffusion prevention layer (130ab) disposed on the lower side of the thermoelectric leg (110). For example, the first-1 diffusion prevention layer (130aa) may be located between the thermoelectric leg (110) and the second-1 diffusion prevention layer (130ba). For example, the first-2 diffusion prevention layer (130ab) may be located between the thermoelectric leg (110) and the second-2 diffusion prevention layer (130bb). The second-1 diffusion prevention layer (130ba) and the second-2 diffusion prevention layer (130bb) may be formed with corresponding thicknesses and materials.

[0102] According to one embodiment, the second diffusion barrier layer (130b) may include a metal powder of one of gold (Au), silver (Ag), tin (Sn), chromium (Cr), platinum (Pt), titanium (Ti), tungsten (W), silicon (Si), manganese (Mn), iron (Fe), cobalt (Co), copper (Cu), or molybdenum (Mo).

[0103] According to one embodiment, the second diffusion barrier layer (130b) may include a layer made of a single metal. For example, the second diffusion barrier layer (130b) may be a single metal layer formed of gold (Au). For example, the second diffusion barrier layer (130b) may be a single metal layer formed of silver (Ag). For example, the second diffusion barrier layer (130b) may be a single metal layer formed of tin (Sn).

[0104] According to one embodiment, the stacked structure of a thermoelectric element (100) comprising a thermoelectric leg (110), a first diffusion prevention layer (130a), and a second diffusion prevention layer (130b) can be designed and modified in various combinations. For example, the thermoelectric element (100) may be composed of a Bi-Te-based thermoelectric leg (110), a first diffusion prevention layer (130a) formed of a nickel (Ni)-chromium (Cr) alloy, and a second diffusion prevention layer (130b) formed of gold (Au). For example, the thermoelectric element (100) may be composed of a Bi-Te-based thermoelectric leg (110), a first diffusion prevention layer (130a) formed of a nickel (Ni)-chromium (Cr) alloy, and a second diffusion prevention layer (130b) formed of silver (Ag). For example, the thermoelectric element (100) may be composed of a Bi-Te thermoelectric leg (110), a first diffusion barrier layer (130a) formed of a nickel (Ni)-chromium (Cr) alloy, and a second diffusion barrier layer (130b) formed of tin (Sn). For example, the thermoelectric element (100) may be composed of a Bi-Te thermoelectric leg (110), a first diffusion barrier layer (130a) formed of a nickel (Ni)-vanadium (V) alloy, and a second diffusion barrier layer (130b) formed of gold (Au). For example, the thermoelectric element (100) may be composed of a Bi-Te thermoelectric leg (110), a first diffusion barrier layer (130a) formed of a nickel (Ni)-vanadium (V) alloy, and a second diffusion barrier layer (130b) formed of silver (Ag). For example, the thermoelectric element (100) may be composed of a Bi-Te-based thermoelectric leg (110), a first diffusion barrier layer (130a) formed of a nickel (Ni)-vanadium (V) alloy, and a second diffusion barrier layer (130b) formed of tin (Sn). However, the stacked configuration of the thermoelectric element (100) described above is merely one embodiment and is not limited thereto; it can be designed and modified in various ways using combinations of various alloy layers and single metal layers.

[0105] According to one embodiment, the second diffusion barrier layer (130b) may be composed of a multi-layer in which a plurality of first single metal layers (133) are stacked. The first single metal layer (133) may include the aforementioned gold (Au), silver (Ag), or tin (Sn). Each of the first single metal layers (133) forming the multi-layer may have a thickness of approximately 30 nm or less. For example, each of the first single metal layers (133) may have a thickness of approximately 1.0 nm to 30.0 nm. For example, each of the first single metal layers (133) may have a thickness of approximately 2.0 nm to 30.0 nm. For example, each of the first single metal layers (133) may have a thickness of approximately 13.0 nm to 15.0 nm.

[0106] According to one embodiment, the second diffusion prevention layer (130b) comprises a plurality of first single metal layers (133) stacked together, and the total thickness of the second diffusion prevention layer (130b) may be the sum of the thicknesses of the first single metal layers (133). According to one embodiment, the total thickness of the second diffusion prevention layer (130b) may be smaller than the total thickness of the first diffusion prevention layer (130a). According to one embodiment, the total thickness of the second diffusion prevention layer (130b) may be smaller than the thickness of the thermoelectric material. The thickness of the second diffusion prevention layer (130b) may be approximately 3.0 μm or less. For example, the thickness of the second diffusion prevention layer (130b) may be approximately 0.01 μm to 3.0 μm. For example, the thickness of the second diffusion prevention layer (130b) may be approximately 0.01 μm to 0.5 μm. For example, the thickness of the second diffusion barrier layer (130b) can be approximately 0.03㎛ to 0.5㎛.

[0107] According to one embodiment, the second diffusion barrier layer (130b) has a structure in which a plurality of first single metal layers (133) are stacked, and can be deposited on the first diffusion barrier layer (130a) by a dry deposition process. For example, the second diffusion barrier layer (130b) may have a structure in which approximately 10 to 300 first single metal layers (133) are stacked. For example, the second diffusion barrier layer (130b) may have a structure in which approximately 50 to 150 first single metal layers (133) are stacked.

[0108] According to one embodiment, internal stress can be minimized by depositing each of the first single metal layers (133) on the upper or lower side of the first diffusion-blocking layer (130a) by a dry deposition process. The thermoelectric element (100) of the present disclosure can minimize internal stress by proceeding with a sputtering process when depositing the first single metal layers (133) on the first diffusion-blocking layer (130a) (or thermoelectric leg (110)), and by forming a multilayer that provides a cooling time for a specified interval after depositing one first single metal layer (133). The minimization of internal stress can improve the long-term durability of the thermoelectric element (100) by increasing the adhesion strength between the first diffusion-blocking layer (130a) and the second diffusion-blocking layer (130b).

[0109] Referring to FIG. 5, an enlarged view of the first diffusion barrier layer (130a) and the second diffusion barrier layer can be seen through analysis equipment. The analysis equipment used is a transmission electron microscope (TEM), which can analyze the internal structure of a material at high resolution using an electron beam. Referring to FIG. 5, the first diffusion barrier layer (130a) deposited on the thermoelectric leg (110) and the second diffusion barrier layer (130b) deposited on the first diffusion barrier layer (130a) are shown, and it can be seen that each of the first diffusion barrier layer (130a) and the second diffusion barrier layer (130b) forms a multi-layer. For example, an interlayer interface can be formed between the first alloy layers (131) constituting the first diffusion barrier layer (130a) and between the first single metal layers (133) constituting the second diffusion barrier layer (130b). The above interface is formed by a cooling time provided at specified intervals during the sputtering process, and the internal stress of the diffusion barrier layer can be minimized. The first diffusion barrier layer (130a) shown in FIG. 5 is a nickel (Ni)-chromium (Cr) alloy layer (or nickel (Ni)-vanadium (V) alloy layer), and the second diffusion barrier layer (130b) was identified as a single metal layer formed of gold (Au).

[0110] According to one embodiment, the thermoelectric element (100) may optionally manufacture a first diffusion prevention layer (130a) and / or a second diffusion prevention layer (130b) forming a multi-layer.

[0111] Referring to FIG. 2, a thermoelectric element (100) can be manufactured with a structure in which a first-1 diffusion prevention layer (130aa) and a second-1 diffusion prevention layer (130ba) are stacked on the upper side of the thermoelectric leg (110), and a first-2 diffusion prevention layer (130ab) and a second-2 diffusion prevention layer (130bb) are stacked on the lower side of the thermoelectric leg (110). The first-1 diffusion prevention layer (130aa) and the second-1 diffusion prevention layer (130ba) are formed from the same material and can be composed of a multi-layer. The first-2 diffusion prevention layer (130ab) and the second-2 diffusion prevention layer (130bb) are formed from the same material and can be composed of a single layer rather than a multi-layer.

[0112] Referring to FIG. 3, a thermoelectric element (100) can be manufactured with a structure in which a first-1 diffusion prevention layer (130aa) and a second-1 diffusion prevention layer (130ba) are stacked on the upper side of the thermoelectric leg (110), and a first-2 diffusion prevention layer (130ab) and a second-2 diffusion prevention layer (130bb) are stacked on the lower side of the thermoelectric leg (110). The first-1 diffusion prevention layer (130aa) and the second-1 diffusion prevention layer (130ba) are formed from the same material and can be composed of multiple layers. The first-2 diffusion prevention layer (130ab) and the second-2 diffusion prevention layer (130bb) are formed from the same material and can be composed of multiple layers.

[0113] According to one embodiment, a diffusion barrier layer (e.g., a first diffusion barrier layer (130a), and a second diffusion barrier layer (130b)) is a layer for restricting diffusion within the solder and may be named at least one of a diffusion blocking layer, a diffusion suppression layer, a barrier layer, a barrier coating layer, a protective layer, a passivation layer, a solder resist layer, and an anti-oxidation layer.

[0114] FIGS. 6a and 6b are flowcharts illustrating a manufacturing process of a thermoelectric element according to one embodiment of the present disclosure.

[0115] FIGS. 7A, 7B, 7C, and 7D are drawings showing equipment for depositing a multilayer diffusion barrier layer during a manufacturing process of a thermoelectric element according to one embodiment of the present disclosure.

[0116] According to one embodiment, a thermoelectric element (e.g., the thermoelectric element (100) of FIGS. 2 and 3) may include a thermoelectric leg (e.g., the thermoelectric leg (110) of FIGS. 2 and 3), a first diffusion prevention layer (e.g., the first diffusion prevention layer (130a) of FIGS. 2 and 3), and / or a second diffusion prevention layer (e.g., the second diffusion prevention layer (130b) of FIGS. 2 and 3).

[0117] The configuration of the thermoelectric element (100) of FIGS. 6a to 7d may be partially or entirely identical to the configuration of the thermoelectric element (100) of FIGS. 1 to 5.

[0118] The embodiments of FIGS. 6a to 7d can be optionally combined with the embodiments of FIGS. 1 to 5 and FIG. 10.

[0119] Referring to FIGS. 6a to 7d, a process for depositing a diffusion barrier layer (130) on a thermoelectric leg (110) of a thermoelectric element (100) is described. The thermoelectric leg (110) may include a P-type thermoelectric leg (110a) and an N-type thermoelectric leg (110b), and the P-type thermoelectric leg (110a) and N-type thermoelectric leg (110b), after the deposition process is completed, may be alternately arranged between electrodes as in FIG. 1.

[0120] According to process 100, a process for preparing a thermoelectric leg (110) can be performed. The thermoelectric leg (110) may be, for example, a Peltier leg. The Peltier leg is a key component used in a thermoelectric module utilizing the Peltier effect, and the Peltier effect is a phenomenon in which heat is absorbed or released when current flows between two types of semiconductors (e.g., P-type and N-type semiconductors), thereby creating a temperature difference.

[0121] According to one embodiment, the thermoelectric leg (110) may be manufactured or selected in a cylindrical shape and in various sizes corresponding to the thermoelectric element (100). For example, the spec of the cylindrical thermoelectric leg (110) may have a size of approximately Φ1.8, H2.3mm or approximately Φ30, H1.9mm.

[0122] According to one embodiment, the material of the thermoelectric leg (110) may include at least one element selected from the group consisting of transition metals, rare earth elements, group 13 elements, group 14 elements, group 15 elements, or group 16 elements. For example, the thermoelectric leg (110) may be made of a composition including at least two of bismuth (Bi), tellurium (Te), cobalt (Co), samarium (Sm), antimony (Sb), indium (In), or cerium (Ce). For example, the thermoelectric leg (110) may be at least one of a Bi-Te system, a Co-Sb system, a Pb-Te system, a Ge-Te system, a Si-Ge system, a Sb-Te system, a Sm-Co system, a transition metal silicide system, a skuttrudite system, a silicide system, or a Half-Whistler system.

[0123] Subsequently, according to process 200, a cleaning process can be performed on the thermoelectric leg (110). For example, by removing foreign substances (e.g., contaminants or dust) from the surface of the Peltier leg, the deposition surface of the Peltier leg can be kept clean before the deposition process. For example, the cleaning process can be performed such that the surface of the thermoelectric leg (110) remains in contact with a cleaning solution (e.g., ethanol concentrate (95% or more)), the immersion time is approximately 3 minutes or more, and the temperature of the cleaning solution is approximately 60°C.

[0124] Subsequently, according to process 300, a process of massaging the cleaned thermoelectric leg (110) with alcohol can be performed. For example, a process of physically cleaning the surface of the Peltier leg using a tool can be performed. The massage tool may be a microfiber brush or a microfiber cloth. The cleaning process can be carried out by rubbing the massage tool on the surface of the Peltier leg and performing a linear reciprocating motion in a horizontal or vertical direction. Through such a cleaning process (e.g., process 200, and process 300), the surface of the thermoelectric leg (110) can be made smooth and the quality of subsequent processes can be ensured.

[0125] Subsequently, according to process 400, a process of introducing the massaged thermoelectric leg (110) into a sputter chamber (300) can be performed. A jig (310) in which the thermoelectric leg (110) can be fixed is placed inside the sputter chamber (300), and the thermoelectric leg (110) can be mounted on the jig (310). The jig (310) can be formed from a material with high heat resistance and mechanical strength, such as aluminum (Al), PEEK (polyether ether ketone), or stainless steel.

[0126] Subsequently, according to process 500, a vacuum formation process can be performed to provide a deposition space within the sputter chamber (300). For example, to facilitate deposition on the surface of the thermoelectric leg (110), the vacuum level of the environmental conditions of the sputter chamber (300) may be approximately 6 x 10 -6 The pressure can be set to torr or less, and Ar (argon) gas can be used as the internal gas. Under the above environmental conditions, the intrusion of external impurities can be prevented and the deposition quality (e.g., the quality of the first diffusion barrier layer (130a) and the second diffusion barrier layer (130b)) can be improved.

[0127] Subsequently, according to process 600, a plasma cleaning process can be performed. The plasma cleaning process can improve the adhesion of the deposition layer (e.g., the first diffusion barrier layer (130a), and the second diffusion barrier layer (130b)) by cleaning surface foreign substances of the thermoelectric leg (110). The plasma cleaning process is a cleaning process that imparts fine irregularities on the surface of the thermoelectric leg (110) and can improve the adhesion of the deposition layer (e.g., the first diffusion barrier layer (130a), and the second diffusion barrier layer (130b)). Plasma cleaning can be performed using O2 or an Ar / O2 mixed gas, with a plasma output of approximately 100 to 200 W, for a processing time of approximately 5 to 10 min.

[0128] Subsequently, according to process 700 (referring to FIGS. 7a and 7b), a first diffusion barrier layer (130a) may be deposited on the upper and / or lower side of the thermoelectric leg (110). For example, the first diffusion barrier layer (130a) may include a first-1 diffusion barrier layer disposed on the upper side of the thermoelectric leg (110) (e.g., the first-1 diffusion barrier layer (130aa) of FIG. 3) and a first-2 diffusion barrier layer disposed on the lower side of the thermoelectric leg (110) (e.g., the first-2 diffusion barrier layer (130ab) of FIG. 3). The first-1 diffusion barrier layer (130aa) and the first-2 diffusion barrier layer (130ab) may be formed with corresponding thicknesses and materials.

[0129] According to one embodiment, the first diffusion barrier layer (130a) may be a Ni-X alloy, wherein X may be at least one of Cr, V, Al, Co, W, Sn, Zn, or Pb. According to one embodiment, the first diffusion barrier layer (130a) may include a nickel (Ni)-chromium (Cr) alloy or a nickel (Ni)-vanadium (V) alloy. For example, according to process 710, the first diffusion barrier layer (130a) may form a structure in which a plurality of nickel (Ni)-chromium (Cr) alloy layers are stacked. For example, according to process 720, the first diffusion barrier layer (130a) may form a structure in which a plurality of nickel (Ni)-vanadium (V) alloy layers are stacked. Process 710 or process 720 may be performed optionally.

[0130] According to one embodiment, the first diffusion barrier layer (130a) is formed by a dry deposition process (e.g., a sputtering process), and the sputtering device for this purpose may include a jig (310) and a first sputtering section (320) spaced apart from the edge portion of the jig (310). Referring to FIGS. 7a and 7b, the jig (310) may include a circular first jig (311) that rotates with a central axis (O) and a second jig (312) disposed on one side of the first jig (311) for fixing a sample (e.g., a thermoelectric leg (110)). For example, the first jig (311) may rotate on its own with respect to the central axis (O). For example, the second jig (312) is fixedly positioned at the edge of the first jig (311), and the first jig (311) can rotate about the central axis (O) in response to rotation while the thermoelectric leg (110) is mounted. The second jig (312) can move past the first sputtering section (320) and the second sputtering section (330).

[0131] According to one embodiment, in process 700, a thermoelectric leg (110) mounted on a second jig (312) moves to be adjacent to a first sputtering section (320), and as the first sputtering section (320) operates, a first diffusion prevention layer (130a) can be deposited on the thermoelectric leg (110). For example, as the thermoelectric leg (110) mounted on the second jig (312) rotates and moves, whenever it is adjacent to the first sputtering section (320) (e.g., when it is located in the first section (A), ON time), one layer of a multilayer (e.g., the first alloy layer (131) of the first diffusion prevention layer (130a)) can be deposited on the thermoelectric leg (110) by the first sputtering process. Subsequently, when the thermoelectric leg (110) mounted on the second jig (312) moves further away from the first sputtering section (320) while rotating, e.g., when it is located in the second section (B), OFF time, a cooling time is provided to one of the layers of the multilayers deposited on the thermoelectric leg (110) (e.g., the first alloy layer (131) of the first diffusion barrier layer (130a)), and the first alloy layer (131) is stably formed so that internal stress can be reduced. The reduction of internal stress can limit (reduce or prevent) physical damage (e.g., cracks, twisting, or warping) to the first diffusion barrier layer (130a). According to one embodiment, the cooling time may be formed to be longer than the deposition time.

[0132] According to one embodiment, the deposition layer (e.g., the first diffusion barrier layer (130a)) formed through the first sputtering section (320) in process 710 may be a multilayer in which a plurality of nickel (Ni)-chromium (Cr) alloy layers are stacked. A single nickel (Ni)-chromium (Cr) alloy layer may be formed when the thermoelectric leg (110) mounted on the second jig (312) rotates once, and the multilayer may be formed by rotating the thermoelectric leg (110) mounted on the second jig (312) multiple times. For example, when the thermoelectric leg (110) mounted on the second jig (312) rotates multiple times, one of the multilayers may be deposited on the thermoelectric leg (110) by the first sputtering process each time it is located in the first section (A) adjacent to the first sputtering section (320) (ON time). The sputtering ON time for depositing a single layer on the thermoelectric leg (110) may be approximately 6.5 ± 2 sec. The alloying amount of chromium (Cr) in the nickel (Ni)-chromium (Cr) alloy layer may be 20 ± 10 wt% relative to the total weight. The alloying amount of Ni (nickel) in the nickel (Ni)-chromium (Cr) alloy layer may be 80 ± 10 wt% relative to the total weight. For example, when the thermoelectric leg (110) mounted on the second jig (312) rotates multiple times, whenever it is located in the second section (B) away from the first sputtering section (320) (OFF time), one of the layers on the thermoelectric leg (110) may have a cooling time by the first sputtering process, thereby reducing internal stress before the next alloy layer is deposited. The cooling time can be controlled by the rotation speed and size of the first jig (311). After a layer is deposited on the thermoelectric leg (110), the subsequent cooling time (OFF time) may be approximately 73.5 ± 10 sec.

[0133] After process 710 is completed, the total thickness of the first diffusion barrier layer (130a), which has a plurality of nickel (Ni)-chromium (Cr) alloy layers stacked thereon, may be approximately 1.0 μm to 10.0 μm. For example, the thickness of the first diffusion barrier layer (130a) may be approximately 3.0 μm to 5.0 μm.

[0134] According to one embodiment, the deposition layer (e.g., the first diffusion barrier layer (130a)) formed through the first sputtering section (320) in process 720 may be a multilayer in which a plurality of nickel (Ni)-vanadium (V) alloy layers are stacked. A single nickel (Ni)-vanadium (V) alloy layer may be formed when the thermoelectric leg (110) mounted on the second jig (312) rotates once, and the multilayer may be formed by rotating the thermoelectric leg (110) mounted on the second jig (312) multiple times. For example, when the thermoelectric leg (110) mounted on the second jig (312) rotates multiple times, one of the multilayers may be deposited on the thermoelectric leg (110) by the first sputtering process each time it is located in the first section adjacent to the first sputtering section (320) (ON time). The sputtering ON time for depositing a single layer on the thermoelectric leg (110) may be approximately 6.5 ± 2 sec. The alloying amount of vanadium (V) in the nickel (Ni)-vanadium (V) alloy layer may be 10 ± 5 wt% relative to the total weight. The alloying amount of Ni (nickel) in the nickel (Ni)-vanadium (V) alloy layer may be 90 ± 5 wt% relative to the total weight. For example, when the thermoelectric leg (110) mounted on the second jig (312) rotates multiple times, whenever it is located in a second section away from the first sputtering section (320) (OFF time), one of the layers on the thermoelectric leg (110) may have a cooling time by the first sputtering process, thereby reducing internal stress before the next alloy layer is deposited. The cooling time can be controlled by the rotation speed and size of the first jig (311). After a layer is deposited on the thermoelectric leg (110), the subsequent cooling time (OFF time) may be approximately 73.5 ± 10 sec.

[0135] After process 720 is completed, the total thickness of the first diffusion barrier layer (130a), which has a plurality of nickel (Ni)-vanadium (V) alloy layers stacked thereon, may be approximately 1.0 μm to 10.0 μm. For example, the thickness of the first diffusion barrier layer (130a) may be approximately 3.0 μm to 5.0 μm.

[0136] Subsequently, according to process 800 (referring to FIG. 7c and FIG. 7d), a second diffusion barrier layer (130b) may be deposited on the upper and / or lower side of the first diffusion barrier layer (130a). For example, the second diffusion barrier layer (130b) may include a second-1 diffusion barrier layer (e.g., second-1 diffusion barrier layer (130ba) of FIG. 3) disposed on the upper side of the first-1 diffusion barrier layer (130aa), and a second-2 diffusion barrier layer (e.g., second-2 diffusion barrier layer (130bb) of FIG. 3) disposed on the lower side of the first-2 diffusion barrier layer (130ab). The second-1 diffusion barrier layer (130ba) and the second-2 diffusion barrier layer (130bb) may be formed with corresponding thicknesses and materials.

[0137] According to one embodiment, the second diffusion barrier layer (130b) may comprise a metal powder of one of gold (Au), silver (Ag), tin (Sn), chromium (Cr), platinum (Pt), titanium (Ti), tungsten (W), silicon (Si), manganese (Mn), iron (Fe), cobalt (Co), copper (Cu), or molybdenum (Mo). According to one embodiment, the second diffusion barrier layer (130b) may comprise a layer made of a single metal. For example, the second diffusion barrier layer (130b) may be a single metal layer formed of gold (Au), silver (Ag), or tin (Sn). For example, according to process 810, the second diffusion barrier layer (130b) may form a structure in which a plurality of single metal layers formed of gold (Au) are stacked. For example, according to process 820, the second diffusion barrier layer (130b) may form a structure in which a plurality of single metal layers formed of tin (Sn) are stacked. Process 810 or process 820 may be performed optionally.

[0138] According to one embodiment, the second diffusion barrier layer (130b) is formed by a dry deposition process (e.g., a sputtering process), and the sputtering device for this purpose may include a jig (310) and a second sputtering section (330) spaced apart from the edge portion of the jig (310). Referring to FIGS. 7c and 7d, the jig (310) may include a circular first jig (311) that rotates with a central axis (O) and a second jig (312) disposed on one side of the first jig (311) for fixing a sample (e.g., a thermoelectric leg (110)). For example, the first jig (311) may rotate on its own with respect to the central axis (O). For example, the second jig (312) is fixedly positioned at the edge of the first jig (311), and the first jig (311) can rotate about the central axis (O) in response to rotation while the thermoelectric leg (110) is mounted. The second jig (312) can move past the first sputtering section (320) and the second sputtering section (330).

[0139] According to one embodiment, in process 800, a thermoelectric leg (110) (or a first diffusion prevention layer (130a)) mounted on a second jig (312) moves to be adjacent to a second sputtering section (330), and as the second sputtering section (330) operates, a second diffusion prevention layer (130b) can be deposited on the first diffusion prevention layer (130a). For example, as the thermoelectric leg (110) (or a first diffusion prevention layer (130a)) mounted on the second jig (312) rotates and moves, whenever it is adjacent to the second sputtering section (330) (e.g., when it is located in the third section (C), ON time), one layer of a multilayer (e.g., a first single metal layer (133) of the second diffusion prevention layer (130b)) can be deposited on the first diffusion prevention layer (130a) by the second sputtering process. Subsequently, when the thermoelectric leg (110) (or the first diffusion prevention layer (130a)) mounted on the second jig (312) is further rotated and moved away from the second sputtering section (330) (e.g., when it is located in the fourth section (D), OFF time), a cooling time is provided to one of the multilayers deposited on the first diffusion prevention layer (130a) (e.g., the first single metal layer (133) of the second diffusion prevention layer (130b)), and the single metal layer (133) is stably formed so that internal stress can be reduced. The reduction of internal stress can limit (reduce or prevent) physical damage (e.g., cracks, twisting, or warping) to the second diffusion prevention layer (130b). According to one embodiment, the cooling time may be formed to be longer than the deposition time.

[0140] According to one embodiment, the deposition layer (e.g., second diffusion prevention layer (130b)) to be formed through the second sputtering section (330) in process 810 may be a multilayer in which a plurality of single Au (gold) metal layers are stacked. A single Au (gold) metal layer may be formed when the thermoelectric leg (110) (or the first diffusion prevention layer (130a)) mounted on the second jig (312) rotates once, and the multilayer may be formed by rotating the thermoelectric leg (110) (or the first diffusion prevention layer (130a)) mounted on the second jig (312) multiple times. For example, when the thermoelectric leg (110) (or the first diffusion prevention layer (130a)) mounted on the second jig (312) rotates multiple times, one layer of the multilayers can be deposited on the first diffusion prevention layer (130a) by the second sputtering process each time it is located in the third section (C) adjacent to the second sputtering section (330) (ON time). The sputtering ON time for depositing one layer on the first diffusion prevention layer (130a) may be approximately 6.5 ± 2 sec. For example, when the thermoelectric leg (110) (or the first diffusion prevention layer (130a)) mounted on the second jig (312) rotates multiple times, one of the layers on the thermoelectric leg (110) may have a cooling time by the second sputtering process whenever it is located in the fourth section (D) away from the second sputtering section (330) (OFF time), thereby reducing internal stress before the next single metal layer is deposited. The cooling time may be longer than the deposition time. The cooling time can be controlled by the rotation speed and size of the first jig (311). After one layer is deposited on the first diffusion prevention layer (130a), the subsequent cooling time (OFF time) may be approximately 73.5 ± 10 sec.

[0141] After process 810 is completed, the total thickness of the second diffusion barrier layer (130b), which is formed by stacking multiple single metal layers of Au (gold), may be approximately 0.01 μm to 3.0 μm. For example, the thickness of the second diffusion barrier layer (130b) may be approximately 0.01 μm to 0.5 μm.

[0142] According to one embodiment, the deposition layer (e.g., second diffusion prevention layer (130b)) to be formed through the second sputtering section (330) in process 820 may be a multilayer in which a plurality of tin (Sn) single metal layers are stacked. A single tin (Sn) single metal layer may be formed when the thermoelectric leg (110) (or the first diffusion prevention layer (130a)) mounted on the second jig (312) rotates once, and the multilayer may be formed by rotating the thermoelectric leg (110) (or the first diffusion prevention layer (130a)) mounted on the second jig (312) multiple times. For example, when the thermoelectric leg (110) (or the first diffusion prevention layer (130a)) mounted on the second jig (312) rotates multiple times, one layer of the multilayers can be deposited on the first diffusion prevention layer (130a) by the second sputtering process each time it is located in the third section (C) adjacent to the second sputtering section (330) (ON time). The sputtering ON time for depositing one layer on the first diffusion prevention layer (130a) may be approximately 6.5 ± 2 sec. For example, when the thermoelectric leg (110) (or the first diffusion prevention layer (130a)) mounted on the second jig (312) rotates multiple times, one of the layers on the thermoelectric leg (110) may have a cooling time by the second sputtering process whenever it is located in the fourth section (D) away from the second sputtering section (330) (OFF time), thereby reducing internal stress before the next single metal layer is deposited. The cooling time may be longer than the deposition time. The cooling time can be controlled by the rotation speed and size of the first jig (311). After one layer is deposited on the first diffusion prevention layer (130a), the subsequent cooling time (OFF time) may be approximately 73.5 ± 10 sec.

[0143] After process 820 is completed, the total thickness of the second diffusion barrier layer (130b), which is formed by stacking multiple single metal layers of tin (Sn), may be approximately 0.01 μm to 3.0 μm. For example, the thickness of the second diffusion barrier layer (130b) may be approximately 0.01 μm to 0.5 μm.

[0144] According to process 900, after the sputtering process is completed, a process of releasing the vacuum inside the chamber and collecting the thermoelectric element (100) can be performed. For example, by slowly releasing the vacuum inside the chamber to balance it with the external atmospheric pressure, damage or defects to the thermoelectric element (100) that may occur due to sudden pressure changes can be prevented. As a condition for releasing the vacuum, the vacuum level inside the chamber is atmospheric pressure, 7.6 x 10⁻⁶ 2 The process can be carried out up to torr, while ensuring that foreign substances inside the chamber do not adhere to the thermoelectric element (100) when the vacuum state is released.

[0145] According to process 1000, a cleaning and inspection process can be performed on a thermoelectric element (100) comprising a diffusion barrier layer (e.g., a first diffusion barrier layer (130a), and / or a second diffusion barrier layer (130b)). The thermoelectric element (100) collected from the sputter chamber (300) can have foreign substances, such as particles, thin film residues, or other impurities remaining on the surface of the thermoelectric element (100), removed, and the cleaning method can be performed using at least one of ultrasonic cleaning, ion water cleaning, or alcohol cleaning. After cleaning is completed, the thermoelectric element (100) can be analyzed to determine whether there are abnormalities, such as the thickness, uniformity, adhesion state, or surface defects of the deposited layer (e.g., thin film). The analysis equipment may include equipment capable of magnifying a portion of the deposited layer, such as an optical microscope or a scanning electron microscope (SEM).

[0146] According to one embodiment, a thermoelectric element (100) advantageous for multilayer formation can be provided by stacking a diffusion prevention layer (130) (e.g., a first diffusion prevention layer (130a), and / or a second diffusion prevention layer (130b)) inline on a thermoelectric leg (110) by a rotary sputtering device. Unlike a rotary sputtering device in which multiple sputtering units are arranged linearly, by placing only one sputtering unit (e.g., a first sputtering unit (320) for the first diffusion prevention layer (130a), and a second sputtering unit (330) for the second diffusion prevention layer (130b)) for forming each diffusion prevention layer, the process can be simplified, equipment can be miniaturized, and / or process costs can be reduced. In addition, the operator can easily adjust the desired thickness of the diffusion prevention layer according to the rotation speed of the jig (310), thereby improving work efficiency.

[0147] FIG. 8 is a graph showing the results of an adhesion strength test between a diffusion prevention layer composed of a single layer and a diffusion prevention layer composed of multiple layers, according to one embodiment of the present disclosure.

[0148] The configuration of the thermoelectric element (100) of FIG. 8 may be partially or entirely identical to the configuration of the thermoelectric element (100) of FIG. 2 to FIG. 7.

[0149] The embodiment of FIG. 8 can be optionally combined with the embodiments of FIG. 1 to 7, FIG. 8, and FIG. 9.

[0150] According to one embodiment, a thermoelectric element (e.g., the thermoelectric element (100) of FIGS. 2 and 3) may include a diffusion prevention layer (e.g., the diffusion prevention layer (130) of FIGS. 2 and 3) forming a multilayer. The thermoelectric element (100) may include a thermoelectric leg (e.g., the thermoelectric leg (110) of FIGS. 2 and 3) (e.g., a Peltier leg), a first diffusion prevention layer (e.g., the first diffusion prevention layer (130a) of FIGS. 2 and 3), and / or a second diffusion prevention layer (e.g., the second diffusion prevention layer (130b) of FIGS. 2 and 3).

[0151] According to one embodiment, the thermoelectric element (100) may include a thermoelectric leg (110) and a first diffusion prevention layer (130a) disposed on the upper or lower side of the thermoelectric leg (110). According to one embodiment, the thermoelectric element (100) may include a thermoelectric leg (110), a first diffusion prevention layer (130a) disposed on the upper or lower side of the thermoelectric leg (110), and a second diffusion prevention layer (130b) disposed on one side of the first diffusion prevention layer (130a).

[0152] According to one embodiment, the first diffusion barrier layer (130a) and / or the second diffusion barrier layer (130b) may form a multilayer. The multilayer of the first diffusion barrier layer (130a) may have a structure in which a plurality of alloy layers formed of a nickel (Ni)-chromium (Cr) alloy or a nickel (Ni)-vanadium (V) alloy are stacked. The multilayer of the second diffusion barrier layer (130b) may have a structure in which a plurality of single metal layers formed of gold (Au), silver (Ag), or tin (Sn) are stacked.

[0153] According to one embodiment, a multilayer of the first diffusion barrier layer (130a) and / or the second diffusion barrier layer (130b) may be formed by a dry deposition process. A multilayer of the first diffusion barrier layer (130a) and / or the second diffusion barrier layer (130b) may be formed by providing a plurality of sputtering processes and a cooling time after the sputtering processes. The cooling time may provide a deposition time during which a multilayer (e.g., alloy layers or single metal layers) of the first diffusion barrier layer (130a) and / or the second diffusion barrier layer (130b) deposited on the first diffusion barrier layer (130a) can be stably formed. Accordingly, physical damage (e.g., cracking, warping, or bending) to the finished thermoelectric element (100) may be limited (reduced or prevented).

[0154] According to one embodiment, the multi-layer of the first diffusion prevention layer (130a) and / or the second diffusion prevention layer (130b) can provide strong adhesive strength compared to a single layer, which is the configuration of a typical thermoelectric element. The strong adhesive strength may occur as the internal stress of the thermoelectric element (100) decreases.

[0155] [Table 1] below shows experimental data values ​​to verify the adhesion of a thermoelectric element in which the diffusion barrier layer is composed of a single layer.

[0156]

[0157] Referring to [Table 1] above, "NO" represents examples of experimental samples. For N-type thermoelectric devices, the tensile strength of a single-layer diffusion barrier was measured using a total of 15 experimental samples, and for P-type thermoelectric devices, the tensile strength of a single-layer diffusion barrier was measured using a total of 24 experimental samples. The tensile strength measurements of N-type thermoelectric devices and P-type thermoelectric devices containing the same type of diffusion barrier (e.g., a deposited layer) showed similar values.

[0158] Referring to [Table 1] and Fig. 8 above, the average value of the converted adhesion force of a thermoelectric element including a single layer of diffusion barrier is 0.333 kgf / mm 2 It was possible to confirm that it was.

[0159] [Table 2] below shows experimental data values ​​to verify the adhesion of a thermoelectric element in which the diffusion barrier layer is composed of multiple layers.

[0160]

[0161] Referring to [Table 2] above, "NO" represents examples of experimental samples. For N-type thermoelectric devices, the tensile strength of the multilayer diffusion barrier layer was measured using a total of 10 experimental samples, and for P-type thermoelectric devices, the tensile strength of the multilayer diffusion barrier layer was measured using a total of 10 experimental samples. The tensile strength measurements of N-type thermoelectric devices and P-type thermoelectric devices containing the same type of diffusion barrier layer (e.g., deposited layer) showed similar values.

[0162] Referring to [Table 2] and Fig. 8 above, the average value of the converted adhesion force of the thermoelectric element including a multilayer diffusion barrier layer is 0.4 kgf / mm 2 It can be confirmed that this is the case. For example, the average value of the converted adhesion force of the thermoelectric element is 0.596 kgf / mm 2 It was possible to confirm that it was.

[0163] Referring to [Table 1], [Table 2], and FIG. 8, it was confirmed that a thermoelectric element composed of a multilayer diffusion barrier layer provides approximately twice the improved adhesion compared to a thermoelectric element composed of a single layer diffusion barrier layer. Accordingly, the thermoelectric element (100) composed of a multilayer diffusion barrier layer of the present disclosure can provide high bonding stability performance by improving (e.g., reducing) internal stress.

[0164] FIG. 9 is a diagram showing a comparative experiment related to the thickness of the first diffusion barrier layer of a thermoelectric element according to one embodiment of the present disclosure.

[0165] The configuration of the thermoelectric element (100) of FIG. 9 may be partially or entirely identical to the configuration of the thermoelectric element (100) of FIG. 2 to FIG. 8.

[0166] The embodiment of FIG. 9 can be optionally combined with the embodiments of FIG. 1 to 8.

[0167] According to one embodiment, a thermoelectric element (e.g., the thermoelectric element (100) of FIGS. 2 and 3) may include a diffusion prevention layer (e.g., the diffusion prevention layer (130) of FIGS. 2 and 3) forming a multilayer. The thermoelectric element (100) may include a thermoelectric leg (e.g., the thermoelectric leg (110) of FIGS. 2 and 3) (e.g., a Peltier leg), a first diffusion prevention layer (e.g., the first diffusion prevention layer (130a) of FIGS. 2 and 3), and / or a second diffusion prevention layer (e.g., the second diffusion prevention layer (130b) of FIGS. 2 and 3).

[0168] According to one embodiment, the first diffusion barrier layer (130a) and / or the second diffusion barrier layer (130b) may form a multi-layer. The multi-layer of the first diffusion barrier layer (130a) may have a structure in which a plurality of alloy layers formed of a nickel (Ni)-chromium (Cr) alloy or a nickel (Ni)-vanadium (V) alloy are stacked. The multi-layer of the second diffusion barrier layer (130b) may have a structure in which a plurality of single metal layers formed of gold (Au), silver (Ag), or tin (Sn) are stacked.

[0169] According to one embodiment, the first diffusion barrier layer (130a) may be deposited with a thickness greater than a certain amount, taking into account soldering with electrodes (e.g., soldering with Sn (tin)). For example, the thickness of the first diffusion barrier layer (130a) may be approximately 3.0 μm or more. For example, the thickness of the first diffusion barrier layer (130a) may be approximately 3.0 μm to 10.0 μm. For example, the thickness of the first diffusion barrier layer (130a) may be approximately 3.0 μm to 5.0 μm.

[0170] Referring to FIG. 9, when the first diffusion barrier layer (130a) placed on the thermoelectric leg (110) is soldered to the electrodes (e.g., soldered with Sn (tin)), it can be seen that the first diffusion barrier layer (130a) remains depending on the thickness. The soldering was performed once by reflow, and the temperature and time were Max 260°C and approximately 1 min, respectively. FIG. 9(a) shows the case where the thickness of the first diffusion barrier layer (130a) is 3.0 μm or more, and FIG. 9(b) shows the case where the thickness of the first diffusion barrier layer (130a) is 1.0 μm or less.

[0171] Referring to FIG. 9(a), it can be seen that after soldering, a portion of the first diffusion prevention layer (130a), which has a thickness of 3.0 μm or more, diffuses into the Sn (tin) layer (410) and another portion stably forms a plating layer (420). It can be seen that a portion of the first diffusion prevention layer (130a) that diffuses into the Sn (tin) layer (410) (e.g., diffusion layer (420a)) forms a relatively blurry layer compared to the plating layer (420) which shows distinct contrast.

[0172] Referring to FIG. 9(b), it can be seen that the first diffusion prevention layer (130a), which has a thickness of 1.0 μm or less (experimental results show that a thickness of Max 0.9 μm to 1.0 μm diffuses into the Sn (tin) layer (410) and disappears), is completely diffused into the Sn (tin) layer (410) and disappears after soldering. The first diffusion prevention layer (130a) that has diffused into the Sn (tin) layer (410) can be identified as a diffusion layer (420b) at the interface of the thermoelectric material (100). If the first diffusion prevention layer (130a) is depleted due to complete diffusion by soldering (e.g., if a plating layer cannot be formed), a decrease in module reliability may occur due to the formation of Sn-Te compounds and brittleness.

[0173] Based on the above experimental results, the first diffusion prevention layer (130a) of the thermoelectric element (100) of the present disclosure can be designed to have a thickness of 3.0 μm (1.0 μm x 300%) or more, taking into account a safety margin of 300%. The first diffusion prevention layer (130a) with a thickness of 3.0 μm or more is not destroyed by soldering (e.g., diffused into a solder layer) and can form a stable layer of the thermoelectric element (100).

[0174] Hereinafter, a general configuration of a refrigerator in which the thermoelectric element (100) of the present disclosure is used is described. However, the thermoelectric element (100) of the present disclosure can be easily modified and applied to various home appliances in which thermoelectric elements are utilized, such as air purifiers, robot vacuum cleaners, cooking appliances, or washing machines, in addition to refrigerators.

[0175] FIG. 10 is a perspective view of a refrigerator according to one embodiment of the present disclosure.

[0176] Referring to FIG. 10, the refrigerator (1) may include a main body (10), a storage room (20), a door (30), and / or a cold air supply device.

[0177] According to one embodiment, the storage room (20) may be partitioned inside the main body (10) and formed into multiple spaces. A door (30) may be positioned at the front of the main body (10) to open and close the storage room (20). A cold air supply device may be provided inside the main body (10) to supply cold air to the storage room (20).

[0178] According to one embodiment, the main body (10) may include an inner housing (11) and / or an outer housing (12). The inner housing (11) may be provided to form, for example, the exterior of the storage room (20). The inner housing (11) may be, for example, made of a plastic material and injection molded integrally. The outer housing (12) may be provided to form, for example, at least a part of the exterior of the refrigerator (1). The outer housing (12) may be made of, for example, a metal material with excellent durability and aesthetic appeal. A receiving space may be formed between the inner housing (11) and the outer housing (12). A main body insulation material (not shown) that insulates the storage room (20) may be provided in part of the receiving space.

[0179] According to one embodiment, a cold air supply device can generate cold air by using a cooling circulation cycle that compresses, condenses, expands, and evaporates a refrigerant.

[0180] According to one embodiment, the storage room (20) may be divided into multiple sections by partitions (14). The storage room (20) may be formed by the internal housing (11) of the main body (10) and the partitions (14). Inside the storage room (20), a plurality of shelves (24) or storage containers (25) may be provided to store food or the like. The plurality of shelves (24) and storage containers (25) may be provided, for example, so as to be separable.

[0181] According to one embodiment, the storage room (20) may be divided into a plurality of storage rooms (21, 22, 23) by a partition wall (14). For example, the storage room (20) may include one first storage room (21) located at the top (e.g., upper storage room) and two second storage rooms (22) (e.g., lower storage rooms) and a third storage room (23) (e.g., lower storage room) located at the bottom, as illustrated.

[0182] According to one embodiment, the partition (14) may include a first partition (141) and a second partition (142). The partition (14) may, for example, have a T-shaped cross-section. The first partition (141) may be provided horizontally, for example, to partition the first storage room (21) and the second and third storage rooms (22, 23). The second partition (142) may be provided vertically, for example, to partition the second storage room (22) and the third storage room (23). The second partition (142) may be formed to protrude downward from the first partition (141), for example. The illustrated second partition (142) is formed protruding from the center of the first partition (141), but is not limited thereto, and the size of the second storage room (22) and the third storage room (23) may vary depending on the position of the second partition (142).

[0183] Among the illustrated storage rooms (20), the first storage room (21) can be used as a refrigerator room, and the second and third storage rooms (22, 23) can be used as freezer rooms, but are not limited thereto, and the location and number of each refrigerator room and freezer room can be varied according to the user's needs.

[0184] According to one embodiment, the number, size, or shape of the storage rooms (20) may vary depending on the shape or location of the partition wall (14). The freezer room may be maintained at approximately minus 20 degrees, and the refrigerator room may be maintained at approximately plus 3 degrees. The storage rooms (20) may be insulated, for example, by the partition wall (14).

[0185] According to one embodiment, the storage room (20) may be divided into left and right sections by a single vertical partition. Here, the vertical partition may be formed such that one end contacts the upper part of the inner housing (11) and the other end contacts the lower part of the inner housing (11). Depending on the position of the vertical partition, the size of the storage room (20) divided into left and right sections may vary. For example, the vertical partition may be provided in the center so that the storage room (20) divided into left and right sections is provided in a mirror-symmetric manner. According to one embodiment, there may be multiple vertical partitions. If there are multiple vertical partitions, three or more storage rooms (20) may be provided in the left and right directions.

[0186] According to one embodiment, the storage room (20) may be divided only into upper and lower sections by a single horizontal partition. That is, the storage room (20) may be divided into two sections, an upper storage room and a lower storage room. Here, the horizontal partition may be formed such that one end contacts the left side of the inner housing (11) and the other end contacts the right side of the inner housing (11). Depending on the position of the horizontal partition, the size of the upper and lower divided storage room (20) may vary. According to one embodiment, there may be multiple horizontal partitions. If there are multiple horizontal partitions, three or more storage rooms (20) may be provided in the upper and lower directions. In addition to the above-described embodiment, multiple storage rooms (20) of various types may be configured depending on the shape and number of the partitions (14).

[0187] According to one embodiment, the door (30) may include a first door (31) (e.g., upper door) or a second door (32) (e.g., lower door) as illustrated. The door (30) may be provided to open and close, for example, an opening (10a) of the main body (10). The first door (31) may be provided as a pair (e.g., double door) to open and close the first storage room (21), for example. The second door (32) may be provided as a pair (e.g., double door) to open and close the second storage room (22) or the third storage room (23), for example. In addition, the number and shape of the door (30) may vary in correspondence with the number and shape of the storage room (20), and the door (30) may be configured to rotate around the hinge (16) as well as to slide.

[0188] According to one embodiment, a rotating bar (316) may be provided on one of the pair of first doors (31). The rotating bar (316) may be positioned, for example, on the side opposite to the side forming the axis of rotation in one of the pair of first doors (31). The rotating bar (316) may be provided, for example, so that the axis of rotation is fixed to the side of one of the pair of first doors (31) and can rotate around the axis of rotation. The rotating bar (316) may be provided, for example, to be positioned in the center of the front of the main body (10) when one of the pair of first doors (31) is closed. The rotating bar (316) can seal the gap between the pair of first doors (31) when the pair of first doors (31) are closed. The main body (10) may be provided with a rotating bar guide (15) that guides the movement of the rotating bar (316) when one of the pair of first doors (31) is closed.

[0189] According to one embodiment, the door (30) (e.g., first door (31) or second door (32)) may include a door panel (30a) or a door body (30b). The door panel (30a) and the door body (30b) may be joined so as to be detachable.

[0190] According to one embodiment, the door body (30b) may be fixed to the main body (10) at one side by a hinge (16), for example. The door body (30b) may be provided to be rotatable relative to the main body (10). The door panel (30a) may form part of the front exterior of the refrigerator (1), for example. The door panel (30a) may be an important aesthetic element, particularly when the refrigerator (1) is placed indoors. Accordingly, the user may customize the front exterior of the refrigerator (1) as desired by replacing the door panel (30a) with one having a different color or design. According to some embodiments, the door panel (30a) and the door body (30b) may be formed as a single unit.

[0191] For convenience of explanation, only one first door (31) and one second door (32) are described below, and the description of the remaining first door (31) and the remaining second door (32) is omitted. However, the first door (31) and the second door (32) for which the description is omitted may each have a configuration approximately identical to that of the first door (31) and the second door (32) described below, except that they are arranged in a mutual mirror-symmetrical manner. Additionally, the second door (32) may have the same configuration as the first door (31), and a detailed description may be omitted.

[0192] According to one embodiment, the first door (31) may include a first door handle (not shown), a first door shelf (313), a first shelf support (314), or a first gasket (315). The first door (31) may be rotatably coupled to the main body (10), for example, to open and close at least a portion of the first storage room (21). A user may open and close the first door (31) using the first door handle. The first door handle may be formed as a recess on the bottom surface of the first door (31) or as a protrusion on the front surface of the first door (31), but is not limited thereto.

[0193] According to one embodiment, the first door shelf (313) may be provided to store food, for example. On both the left and right sides of the first door shelf (313), a first shelf support (314) may be provided to support the first door shelf (313). The first shelf support (314) may be formed to extend vertically from the first door (31), for example. That is, the first shelf support (314) may be provided to protrude rearward from the back surface of the first door (31) and extend in the vertical direction. The first shelf support (314) may be provided detachably to the first door (31) as a separate component, for example, or may be formed integrally. The first shelf support (314) may be formed to protrude rearward from the rear surface of the door body (30b), for example.

[0194] According to one embodiment, the first gasket (315) may be provided to wrap around the back edge of the first door (31), for example. Specifically, the first gasket (315) may be provided to wrap around the edge of the door body (30b). The first gasket (315) may be provided to seal the gap with the main body (10) when the first door (31) is closed.

[0195] According to one embodiment, the second door (32) may include a second door handle (321) or a second gasket (322). The second door (32) may be rotatably coupled to the main body (10), for example, to open and close the second storage room (22) or the third storage room (23). A user may open and close the second door (32) using the second door handle (321). The second door handle (321) may be formed as a recess on the upper surface of the second door (32) or as a protrusion on the front surface of the second door (32), but is not limited thereto.

[0196] According to one embodiment, the second gasket (322) may be provided to wrap around, for example, the back edge of the second door (32). The second gasket (322) may be provided to seal the gap with the main body (10) when the second door (32) is closed.

[0197] Although not illustrated, the second door (31) may further include a configuration that is wholly or partially identical to the first door shelf (313) and the first shelf support (314) of the first door (32).

[0198] According to one embodiment, the refrigerator (1) may include a top table (13) provided on the upper part of the main body (10). The top table (13) may be coupled to the upper part of the outer housing (12). For example, the top table (13) may be coupled to the upper surface of the outer housing (12). For example, the top table (13) may be fixed to the outer housing (12).

[0199] According to one embodiment, the top table (13) can cover the hinge bracket (40) of the upper door. In this respect, the top table (13) can be named a hinge bracket cover.

[0200] According to one embodiment, the top table (13) can cover various electrical components. A receiving space for accommodating various electrical components may be formed on the inside of the top table (13). For example, the top table (13) can cover a door drive unit (400) described later, and the door drive unit (400) can be accommodated on the inside of the top table (13). In this respect, the top table (13) may be named a door drive unit cover.

[0201] Although the refrigerator (1) according to one embodiment of the present disclosure has been described as an example of the present disclosure on the premise that it is a cold-cooling refrigerator, the concept of the present disclosure is not limited thereto and can also be applied to a direct-cooling refrigerator.

[0202] Generally, a thermoelectric element may include thermoelectric legs classified into N-type and P-type, and electrodes electrically connected to the thermoelectric legs. Soldering may be performed on the thermoelectric legs to connect them to the electrodes. If one side of the thermoelectric leg is directly soldered to the electrode, an intermetallic compound (IMC) is formed due to thermal diffusion, which causes brittleness (e.g., increased internal stress) in the thermoelectric leg and can frequently lead to device failure.

[0203] To reduce internal stress of the above thermoelectric element, a diffusion barrier layer may be placed on the thermoelectric leg; however, a conventional diffusion barrier layer (e.g., a single-layer diffusion barrier layer) has poor adhesion strength with the thermoelectric leg, which may result in reduced durability.

[0204] A thermoelectric element according to one embodiment of the present disclosure can provide a stable thermoelectric element by depositing a plurality of diffusion barrier layers on a thermoelectric leg through a dry deposition process.

[0205] A thermoelectric element according to one embodiment of the present disclosure can provide a thermoelectric element with improved durability by reducing internal stress and increasing the adhesion strength between the diffusion barrier layer and the thermoelectric leg by forming a diffusion barrier layer formed of a multi-layer (e.g., a layer in which a plurality of alloy layers and / or a single metal layer are stacked).

[0206] A thermoelectric element according to one embodiment of the present disclosure includes a diffusion barrier layer, and the diffusion barrier layer may provide a multi-layer in which a plurality of alloy layers formed of a nickel (Ni)-chromium (Cr) alloy or a nickel (Ni)-vanadium (V) alloy are stacked. The diffusion barrier layer may form a thermoelectric element with improved (reduced) internal stress.

[0207] A thermoelectric element according to one embodiment of the present disclosure includes a diffusion barrier layer, and the diffusion barrier layer may provide a multi-layer of a plurality of single metal layers formed of gold (Au), silver (Ag), or tin (Sn). The diffusion barrier layer may form a thermoelectric element with improved (reduced) internal stress.

[0208] A thermoelectric element according to one embodiment of the present disclosure provides a diffusion barrier layer through a dry deposition process, thereby eliminating an insulating film on the side of the thermoelectric element. Accordingly, the thermoelectric element can provide a simplified manufacturing process, improved productivity, reduced costs due to lower manufacturing costs, and an environmentally friendly process.

[0209] A thermoelectric element according to one embodiment of the present disclosure forms a diffusion barrier layer that forms a multilayer, thereby improving (reducing) internal stress and, accordingly, can provide stable and efficient performance of a home appliance (e.g., refrigerator).

[0210] The effects obtainable from the present disclosure are not limited to those mentioned above, and other unmentioned effects will be clearly understood by those skilled in the art to which the present disclosure belongs from the description below.

[0211] A thermoelectric element (100) according to one embodiment of the present disclosure may include a Bi-Te-based thermoelectric leg (110), a first diffusion prevention layer (130a) comprising a plurality of stacked alloy layers (131) disposed on the upper and / or lower side of the thermoelectric leg, wherein each of the stacked alloy layers (131) has a thickness of 1 nm to 30 nm and comprises a first diffusion prevention layer (130a) comprising a nickel (Ni)-chromium (Cr) alloy or a nickel (Ni)-vanadium (V) alloy, and a second diffusion prevention layer (130b) disposed on one side of the first diffusion prevention layer and comprising gold (Au), silver (Ag), tin (Sn), or a combination thereof.

[0212] According to one embodiment, the second diffusion barrier layer (130b) comprises a multi-layer including a plurality of stacked single metal layers (133), each of the stacked single metal layers (133) may comprise gold (Au), silver (Ag), tin (Sn), or a combination thereof, and may have a thickness of 1 nm to 30 nm.

[0213] According to one embodiment, each of the stacked alloy layers (131) may have a thickness of 13 nm to 15 nm, or each of the stacked single metal layers (133) may have a thickness of 13 nm to 15 nm.

[0214] According to one embodiment, in the nickel (Ni)-chromium (Cr) alloy of the first diffusion barrier layer (130a), the chromium (Cr) content may be 20 ± 10 wt % relative to the total weight of the nickel (Ni)-chromium (Cr) alloy.

[0215] According to one embodiment, in the nickel (Ni)-vanadium (V) alloy of the first diffusion barrier layer (130a), the content of vanadium (V) may be 10 ± 5 wt % relative to the total weight of the nickel (Ni)-vanadium (V) alloy.

[0216] According to one embodiment, the thickness of the first diffusion prevention layer (130a) may be greater than the thickness of the second diffusion prevention layer (130b).

[0217] According to one embodiment, the first diffusion barrier layer (130a) may have a thickness of 1.0 μm to 10.0 μm.

[0218] According to one embodiment, the first diffusion barrier layer (130a) may have a thickness of 3.0 μm to 5.0 μm.

[0219] According to one embodiment, the second diffusion barrier layer (130b) may have a thickness of 0.01 μm to 3.0 μm.

[0220] According to one embodiment, the first diffusion prevention layer (130a) and / or the second diffusion prevention layer (130b) may be formed by a dry deposition process.

[0221] According to one embodiment, in the dry deposition process, when forming a multilayer of the first diffusion prevention layer (130a) or the second diffusion prevention layer (130b), the cooling time may be configured to be longer than the deposition time of the sputtering process.

[0222] According to one embodiment, the first diffusion prevention layer (130a) may include a first-1 diffusion prevention layer (130aa) deposited on the upper surface of the thermoelectric leg (110) and a first-2 diffusion prevention layer (130ab) deposited on the lower surface of the thermoelectric leg (110).

[0223] According to one embodiment, the second diffusion prevention layer (130b) may include a second-1 diffusion prevention layer (130ba) deposited on the upper surface of the first-1 diffusion prevention layer (130aa), and a second-2 diffusion prevention layer (130bb) deposited on the lower surface of the first-2 diffusion prevention layer (130ab).

[0224] According to one embodiment, the adhesion strength of the multilayer of the first diffusion prevention layer (130a) may have a value of 0.4 kgf / mm2 or more.

[0225] A refrigerator (1) according to one embodiment of the present disclosure may include a main body (10), a door (30) rotatably connected to open and close the main body, a storage room (20) disposed inside the main body for storing food, and a cold air supply device including a thermoelectric element (100) configured to supply cold air to the storage room. The thermoelectric element (100) may include a Bi-Te-based thermoelectric leg (110), a first diffusion prevention layer (130a) comprising a plurality of stacked alloy layers (131) disposed on the upper and / or lower side of the thermoelectric leg, wherein each of the stacked alloy layers (131) comprises a first diffusion prevention layer (130a) comprising a nickel (Ni)-chromium (Cr) alloy or a nickel (Ni)-vanadium (V) alloy, and a second diffusion prevention layer (130b) disposed on one side of the first diffusion prevention layer comprising gold (Au), silver (Ag), tin (Sn), or a combination thereof.

[0226] According to one embodiment, the second diffusion barrier layer (130b) comprises a multi-layer including a plurality of stacked single metal layers (133), and each of the stacked single metal layers (133) may include gold (Au), silver (Ag), tin (Sn), or a combination thereof.

[0227] According to one embodiment, each of the stacked alloy layers (131) may have a thickness of 13 nm to 15 nm, or each of the plurality of single metal layers (133) may have a thickness of 13 nm to 15 nm.

[0228] According to one embodiment of the present disclosure, a method for manufacturing a thermoelectric element (100) comprises a Bi-Te-based thermoelectric leg (110), a first diffusion prevention layer (130a) on one side of the thermoelectric leg comprising a multi-layer including a plurality of stacked alloy layers (131), wherein each of the stacked alloy layers (131) comprises a nickel (Ni)-chromium (Cr) alloy or a nickel (Ni)-vanadium (V) alloy, a first diffusion prevention layer (130a), and a second diffusion prevention layer (130b) disposed on one side of the first diffusion prevention layer and comprising gold (Au), silver (Ag), tin (Sn), or a combination thereof, the method comprising a plasma cleaning process of the thermoelectric leg (110), a process of depositing the first diffusion prevention layer (130a) on the thermoelectric leg (110) through a first sputtering unit, and a process on the first diffusion prevention layer (130a) through a second sputtering unit The process may include depositing a second diffusion barrier layer (130b).

[0229] According to one embodiment, in the process of forming the first diffusion barrier layer, the thermoelectric leg is mounted on a rotating jig and can rotate multiple times.

[0230] According to one embodiment, the alloy layer may be formed on the thermoelectric leg by sputtering in a first section (A) adjacent to the first sputtering section.

[0231] According to one embodiment, in a second section (B) where the thermoelectric leg is far from the first sputtering section, a cooling time is provided so that the internal stress of the alloy layer can be reduced.

[0232] According to one embodiment, the cooling time of the second section may be longer than the time during which the alloy layer of the first section is formed.

[0233] According to one embodiment, in the process of forming the second diffusion prevention layer, the thermoelectric leg and the first diffusion prevention layer can be mounted on a rotating jig and rotated multiple times.

[0234] According to one embodiment, a single metal layer may be formed on the first diffusion prevention layer by sputtering in a third section (C) adjacent to the second sputtering section of the first diffusion prevention layer.

[0235] According to one embodiment, a cooling time is provided in a fourth section (D) away from the second sputtering section of the first diffusion-blocking layer, so that the internal stress of the single metal layer can be reduced.

[0236] According to one embodiment, the cooling time of the fourth section may be longer than the time during which the single metal layer of the third section is formed.

Claims

1. In a thermoelectric element (100), Bi-Te thermoelectric leg (110); A first diffusion barrier layer (130a) comprising a multi-layer having a plurality of stacked alloy layers (131) disposed on the upper and / or lower side of the thermoelectric leg, wherein each of the stacked alloy layers (131) has a thickness of 1 nm to 30 nm and comprises a nickel (Ni)-chromium (Cr) alloy or a nickel (Ni)-vanadium (V) alloy; and A thermoelectric element comprising a second diffusion prevention layer (130b) disposed on one side of the first diffusion prevention layer and comprising gold (Au), silver (Ag), tin (Sn), or a combination thereof.

2. In Paragraph 1, The second diffusion prevention layer (130b) comprises a multi-layer including a plurality of stacked single metal layers (133), and Each of the stacked single metal layers (133) comprises gold (Au), silver (Ag), tin (Sn), or a combination thereof, and has a thickness of 1 nm to 30 nm, forming a thermoelectric element.

3. In Paragraph 1 or 2, A thermoelectric element, wherein each of the above-mentioned stacked alloy layers (131) has a thickness of 13 nm to 15 nm, or each of the above-mentioned stacked single metal layers (133) has a thickness of 13 nm to 15 nm.

4. In any one of paragraphs 1 to 3, A thermoelectric element in which, in the nickel (Ni)-chromium (Cr) alloy of the first diffusion barrier layer (130a), the chromium (Cr) content is 20 ± 10 wt % relative to the total weight of the nickel (Ni)-chromium (Cr) alloy.

5. In any one of paragraphs 1 to 3, A thermoelectric element in which, in the nickel (Ni)-vanadium (V) alloy of the first diffusion barrier layer (130a), the vanadium (V) content is 10 ± 5 wt % relative to the total weight of the nickel (Ni)-vanadium (V) alloy.

6. In any one of paragraphs 1 through 5, A thermoelectric element in which the thickness of the first diffusion prevention layer (130a) is greater than the thickness of the second diffusion prevention layer (130b).

7. In any one of paragraphs 1 through 6, A thermoelectric element having a thickness of 1.0 μm to 10.0 μm for the first diffusion prevention layer (130a).

8. In any one of paragraphs 1 through 7, A thermoelectric element having a thickness of 3.0 μm to 5.0 μm for the first diffusion prevention layer (130a).

9. In Paragraph 8, A thermoelectric element having a thickness of 0.01 μm to 3.0 μm for the second diffusion prevention layer (130b).

10. In any one of paragraphs 1 through 9, The thermoelectric element, wherein the first diffusion prevention layer (130a) and / or the second diffusion prevention layer (130b) are formed by a dry deposition process.

11. In Paragraph 10, A thermoelectric element configured to perform a cooling time longer than the deposition time of the sputtering process when forming a multilayer of the first diffusion prevention layer (130a) or the second diffusion prevention layer (130b) in the above dry deposition process.

12. In any one of paragraphs 1 through 11, The thermoelectric element, wherein the first diffusion prevention layer (130a) comprises a first-1 diffusion prevention layer (130aa) deposited on the upper surface of the thermoelectric leg (110) and a first-2 diffusion prevention layer (130ab) deposited on the lower surface of the thermoelectric leg (110).

13. In Paragraph 12, The thermoelectric element, wherein the second diffusion prevention layer (130b) comprises a second-1 diffusion prevention layer (130ba) deposited on the upper surface of the first-1 diffusion prevention layer (130aa) and a second-2 diffusion prevention layer (130bb) deposited on the lower surface of the first-2 diffusion prevention layer (130ab).

14. In any one of paragraphs 1 through 12, A thermoelectric element having a multilayer adhesion strength of the first diffusion prevention layer (130a) of the above-mentioned thermoelectric element having a value of 0.4 kgf / mm2 or more.

15. In the refrigerator (1), Main body (10); A door (30) rotatably connected to open and close the main body; A storage room (20) disposed inside the main body and for storing food; and A cold air supply device configured to supply cold air to the above storage room and including a thermoelectric element (100), The above thermoelectric element (100) is, Bi-Te thermoelectric leg (110); A first diffusion prevention layer (130a) comprising a multi-layer having a plurality of stacked alloy layers (131) disposed on the upper and / or lower side of the thermoelectric leg, wherein each of the stacked alloy layers (131) comprises a nickel (Ni)-chromium (Cr) alloy or a nickel (Ni)-vanadium (V) alloy; and A refrigerator comprising a second diffusion prevention layer (130b) disposed on one side of the first diffusion prevention layer and comprising gold (Au), silver (Ag), tin (Sn), or a combination thereof.

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