KR101208065B1 - A Manufacturing Method of Thermolectric Semiconductor - Google Patents

Abstract

The present invention relates to a method of manufacturing a thermoelectric semiconductor including a thermoelectric semiconductor device, wherein the thermoelectric semiconductor device is electrodeposited by an electrochemical method. By electrodeposition by this, the damage of a thermoelectric semiconductor element by high temperature and high pressure can be prevented.

Description

A manufacturing method of thermolectric semiconductor

The present invention relates to a method for manufacturing a thermoelectric semiconductor, and more particularly, to a method for manufacturing a thermoelectric semiconductor that can proceed the process under the conditions of room temperature and atmospheric pressure.

In general, thermoelectric semiconductor modules are used for optical communication semiconductor lasers, charge coupled device (CCD) cameras, photomultipliers, various thermographs, infrared gas analyzers, black body standard thermoplates, and heat tracking missile sensors in the optoelectronic field. It is used in thermo-process bath for semiconductor process, thermo-plate for semiconductor process, circulator for semiconductor process, and large scale integrated circuit (LSI) temperature cycle tester, and is used for instant cold / hot water purifier and kimchi refrigerator of general household electronics. It is possible to maintain the proper or to be applied as a generator by the temperature difference.

On the other hand, a phenomenon relating to the change between thermal energy and electrical energy is generally called a thermoelectric phenomenon, which has a Seebeck effect and a Peltier effect.

Seebeck Effeck is a loop that connects two ends of two different kinds of materials, such as antimony (Sb) and bismuth (Bi), respectively, to create a loop, and one connection point to high temperature, and the other connection point to low temperature. When the current flows, the Peltier Effect, on the other hand, refers to a phenomenon in which heat is generated or absorbed when current flows to junctions of different materials.

Hereinafter, the term thermoelectric semiconductor may be used as a generic term for a semiconductor module that converts electrical energy into thermal energy or vice versa by using the Seebeck effect and the Peltier effect.

Thermoelectric semiconductor in the thermoelectric semiconductor module using this phenomenon is the phenomenon that the electromotive force is generated due to the movement of the carrier inside the device when there is a temperature difference across the device, or the opposite phenomenon, it is eco-friendly noise-free cooling and pollution-free electric power generation Is making it possible.

Among them, the principle of thermoelectric semiconductor using the Seebeck effect is that if a temperature difference occurs at both ends of a fixed metal rod, for example, in the case of n-type, the electrons in the hot end have higher kinetic energy than the electrons in the cold end. The electrons in the hot end are diffused into the cold end to lower the energy because the electrons in the hot end are on average higher than the Fermi lever.

In addition, as the electrons move to the low temperature stage, the low temperature stage is charged with "-", and the high temperature portion is charged with "+" to generate a potential difference between both ends of the metal rod. This potential difference is called thermoelectromotive force. .

In this case, in forming an n-type thermoelectric element and a p-type thermoelectric element, a CSVT (Close Space Vapor Transport) method, a co-evaporation method, or a MOCVD method is generally used.

However, in the method of forming a general thermoelectric element as described above, the deposition temperature is high, and the deposition process is performed at a high pressure, and thus there is a problem in that the thermoelectric semiconductor module is damaged by high temperature and high pressure, and there is a difficulty in manufacturing the module.

The problem to be solved by the present invention is to provide a method of manufacturing a thermoelectric semiconductor that can proceed the process under the conditions of room temperature and atmospheric pressure.

The objects of the present invention are not limited to the above-mentioned objects, and other objects not mentioned can be clearly understood by those skilled in the art from the following description.

In order to solve the above-mentioned problems, the present invention provides a method of manufacturing a thermoelectric semiconductor including a thermoelectric semiconductor device, wherein the thermoelectric semiconductor device is electrodeposited by an electrochemical method.

Further, the thermoelectric semiconductor device according to the present invention is characterized in that the thermoelectric semiconductor device comprises one or two elements selected from the group consisting of bismuth (Bi) and antimony (Sb) of Group 5B and one kind or two kinds of elements selected from Tellurium (Te) and selenium Or a complex compound composed of two kinds of elements. The present invention also provides a method of manufacturing a thermoelectric semiconductor.

The present invention also provides a method of manufacturing a thermoelectric semiconductor, wherein the thermoelectric semiconductor element is an alloy having a composition in which the ratio of the number of atoms in the group 5B and the number of atoms in the group 6B is 2 ± 0.5: 3 ± 0.5. .

The present invention also provides a method of manufacturing a thermoelectric semiconductor device, wherein the thermoelectric semiconductor device includes a P-type thermoelectric semiconductor device and an N-type thermoelectric semiconductor device.

In the electrochemical method, the substrate is supported on a liquid electrolyte containing ions for forming the thermoelectric semiconductor element by using the substrate as a working electrode, and a constant current or voltage is applied using the counter electrode and the reference electrode. And a constant voltage is applied to the thermoelectric semiconductor.

The present invention also provides a method of manufacturing a thermoelectric semiconductor, wherein the working electrode is a substrate on which a metal electrode having a structure of Ni / Au laminated on a silicon substrate by a sputtering method is formed.

The present invention also provides a method of manufacturing a thermoelectric semiconductor, wherein the liquid electrolyte further comprises a surfactant.

In addition, the present invention provides a method for manufacturing a thermoelectric semiconductor, characterized in that the surfactant comprises an anionic surfactant, cationic surfactant or nonionic surfactant.

Further, the present invention is characterized in that the liquid electrolyte includes a liquid electrolyte for forming a P-type thermoelectric semiconductor element or a liquid electrolyte for forming an N-type thermoelectric semiconductor element, and the composition of the liquid electrolyte for forming the P- And a liquid electrolyte for forming the N-type thermoelectric semiconductor device include a cationic surfactant.

The present invention also provides a method of manufacturing a thermoelectric semiconductor, wherein the cationic surfactant is CTAB (Cetyl Trimethyl Ammonium Bromide).

The present invention also provides a method of manufacturing a thermoelectric semiconductor, wherein the liquid electrolyte further comprises at least one material selected from the group consisting of Ag, Cu, Pb, Sn and Ge.

According to the method for manufacturing a thermoelectric semiconductor according to the present invention as described above, by electrodepositing the thermoelectric semiconductor device by an electrochemical method, there is an effect that can prevent damage to the thermoelectric semiconductor device by high temperature and high pressure.

In the electrodeposition of the thermoelectric semiconductor element by the electrochemical method, the present invention can further improve the performance index of the thermoelectric semiconductor by further including a surfactant in the composition of the liquid electrolyte.

1 is a schematic perspective view illustrating a thermoelectric semiconductor according to the present invention.
2 is a schematic view showing an electrodeposition process by the electrochemical method according to the present invention.
FIGS. 3A and 3B are views showing a P-type thermoelectric semiconductor device formed by an electrochemical method according to a first condition of the present invention. FIG.
4A and 4B are views showing a P-type thermoelectric semiconductor element formed by an electrochemical method according to a second condition of the present invention.
5A and 5B are views showing a P-type thermoelectric semiconductor device formed by an electrochemical method according to a third condition of the present invention.
FIG. 6 is a Seebeck coefficient of a thermoelectric semiconductor including a P-type thermoelectric semiconductor device according to the first to third conditions and an N-type thermoelectric semiconductor device according to a fourth condition, and a power factor thereof according to the present invention. Factor) is a graph showing the change.

Advantages and features of the present invention, and methods of achieving the same will become apparent with reference to the embodiments described below in detail in conjunction with the accompanying drawings. The present invention may, however, be embodied in many different forms and should not be construed as being limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. Is provided to fully convey the scope of the invention to those skilled in the art, and the invention is only defined by the scope of the claims.

DETAILED DESCRIPTION Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. &Quot; and / or "include each and every combination of one or more of the mentioned items. ≪ RTI ID = 0.0 >

Although the first, second, etc. are used to describe various components, it goes without saying that these components are not limited by these terms. These terms are used only to distinguish one component from another. Therefore, it goes without saying that the first component mentioned below may be the second component within the technical scope of the present invention.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In the present specification, the singular form includes plural forms unless otherwise specified in the specification. The terms " comprises "and / or" comprising "used in the specification do not exclude the presence or addition of one or more other elements in addition to the stated element.

Unless otherwise defined, all terms (including technical and scientific terms) used in the present specification may be used in a sense that can be commonly understood by those skilled in the art. Also, commonly used predefined terms are not ideally or excessively interpreted unless explicitly defined otherwise.

The terms spatially relative, "below", "beneath", "lower", "above", "upper" And can be used to easily describe a correlation between an element and other elements. Spatially relative terms should be understood in terms of the directions shown in the drawings, including the different directions of components at the time of use or operation. For example, when inverting an element shown in the figures, an element described as "below" or "beneath" of another element may be placed "above" another element . Thus, the exemplary term "below" can include both downward and upward directions. The components can also be oriented in different directions, so that spatially relative terms can be interpreted according to orientation.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.

1 is a schematic perspective view illustrating a thermoelectric semiconductor according to the present invention.

The apparatus for thermoelectric cooling, thermoelectric heating and thermoelectric power generation using the thermoelectric characteristics of the thermoelectric semiconductor are all basic configurations. As shown in FIG. 1, the P-type thermoelectric semiconductor element 2 and the N-type thermoelectric semiconductor are shown in FIG. 1. The element 3 may be bonded to each other with the metal electrode 4 interposed therebetween, so that a thermoelectric module 1 formed by forming a pair of PN elements may be connected in series. At this time, the metal electrode 4 may be formed on a separate support substrate (not shown) by sputtering.

That is, the thermoelectric semiconductor according to the present invention may include two layers of support substrates (not shown) arranged in parallel at intervals up and down, and metal electrodes may be formed on the respective support substrates by sputtering. have. In this case, the support substrate may be a silicon substrate or an alumina (Al ₂ O ₃ ) substrate, the metal electrode may be used a common metal, specifically, a single film or a multilayer film such as Cu, Ni, Au, Ag, etc. Can be. Since this is obvious in the art, the following detailed description will be omitted.

In addition, the thermoelectric semiconductor device materials for forming the thermoelectric semiconductor devices 2 and 3 include one or two elements selected from bismuth (Bi) and antimony (Sb), which are Group 5B, tellurium (Te), and Group 6B. It may include a compound compound consisting of one or two elements selected from selenium (Se), the ratio of the number of atoms of mainly Group 5B (Bi and Sb) and the number of atoms of Group 6B (Te and Se) 2 Alloys with a composition of ± 0.5: 3 ± 0.5.

For example, as thermoelectric semiconductor devices, Bi ₂ Te ₃ , Bi ₂ Se ₃ , Sb ₂ Te ₃ , and the like having excellent thermoelectric functions may be used. However, the present invention does not limit the type of thermoelectric semiconductor devices. General thermoelectric semiconductor devices used in the industry may be used.

In the thermoelectric semiconductor as described above, when a temperature difference exists between both ends of the device, electromotive force is generated due to the movement of a carrier within the device.

That is, when the temperature difference occurs at both ends of the metal electrode, in the n-type, the electrons in the high end have higher kinetic energy than the electrons in the low end, so that the electrons in the high end have an average Fermi level ( Because of the higher energy state than the Fermi lever, electrons in the hot end diffuse into the cold end to lower the energy.

In addition, as the electrons move to the low temperature stage, the low temperature stage is charged with "-", and the high temperature portion is charged with "+" to generate a potential difference between both ends of the metal electrode. Will occur.

At this time, in general, the thermoelectric performance of a material used in the production of a thermoelectric semiconductor can be evaluated by the following equation.

Where ZT: performance index, α: Seebeck coefficient, σ: electrical conductivity, κ: thermal conductivity, and ρ: specific resistance.

Therefore, in order to improve the thermoelectric performance (performance index: ZT) of the thermoelectric semiconductor material, the raw material alloy material which increases the value of the Seebeck coefficient (α) or the electrical conductivity (σ) or decreases the thermal conductivity (κ) or the specific resistance (ρ). You can see that it is good to use. This will be described later.

Subsequently, a method of forming the thermoelectric semiconductor elements 2 and 3 of the thermoelectric semiconductor according to the present invention will be described.

In the present invention, the thermoelectric semiconductor devices 2 and 3 are electrodeposited by an electrochemical method.

Electrodeposition by the electrochemical method, as can be seen in Figure 2 showing a schematic electrodeposition process by the electrochemical method, ions for forming the thermoelectric semiconductor element using the substrate as the working electrode 100 After supporting the substrate in the liquid electrolyte 200 including a, refers to a method of applying a constant current or a constant voltage using the counter electrode 210 and the reference electrode 220.

Specifically, the electrochemical method may use the constant current method, the electrostatic potential method, the circulating current method, and the like, and each method may adjust each factor to freely control the thickness of the thermoelectric semiconductor device.

For example, in the constant current method, the applied current is in the range of 0.01 to -100 mA / cm 2, the current application time is in the range of 1 minute to 500 minutes, and the potentiostatic method has an applied potential in the range of 0.1 to 1.5 V, and the potential application time. The circulating current method has a potential scanning speed in the range of 1 to 1000 mV / s, and the cyclic potential recovery can be performed in the range of 1 to 500 minutes.

At this time, the electrochemical method is typically carried out at room temperature and normal pressure, which can maintain mild conditions compared to the high temperature, high pressure process generally proceeds.

Meanwhile, the working electrode may be a substrate on which a metal electrode having a structure in which Ni / Au is laminated by a sputtering method is formed on a silicon substrate. A substrate that is conductive and does not react with an electrolyte is suitable. Silver, titanium (Ti), nickel (Ni), molybdenum (Mo), cadmium (Cd), platinum (Pt), gold (Au), indium-tin-oxide (ITO), glass, stainless steel and Each may be appropriately selected from a carbon substrate and the like. Also, in general, the reference electrode may use Ag / AgCl.

Table 1 is a chart comparing the characteristics of the thermoelectric semiconductor device deposition method and the thermoelectric semiconductor device according to the present invention.

Deposition method Deposition temperature (℃) Seebeck coefficient (μV / K) References CSVT (Close Space Vapor Transport) Method 450 108 Semicond. Sci. Technol. 24 025025 (2009) Co-Deposition 1
(co-evaporation) 260 170 Thin Solid Films
408 270 (2002) Co-Deposition 2
(co-evaporation) 240 153 Vacuum 82 1499 (2008) MOCVD method 350 115 Journal of Crystal Growth 170 817 (1997) Electrochemical method Room temperature (about 10-25) 118 Invention

That is, as can be seen from Table 1, in forming a thermoelectric semiconductor device, a CSVT (Close Space Vapor Transport) method, a co-evaporation method, or a MOCVD method is generally used.

At this time, although the formation of the thermoelectric semiconductor device by the electrochemical method according to the present invention tends to lower a certain part of the Seebeck coefficient as compared with the co-deposition method, the Seebeck coefficient is higher than that of the CSVT method or the MOCVD method.

In particular, in the case of a general method of forming a thermoelectric element, the deposition temperature is high, and the deposition process is performed in a vacuum state, but the electrochemical method according to the present invention is generally performed at room temperature and atmospheric pressure, which is generally performed at high temperature, Mild conditions can be maintained compared to high pressure processes.

Therefore, in the present invention, since the process of forming the thermoelectric semiconductor device is performed at low temperature and atmospheric pressure conditions compared to the high temperature and high pressure processes which are generally performed, damage to the thermoelectric semiconductor device due to high temperature and high pressure can be prevented.

FIGS. 3A and 3B are views showing a P-type thermoelectric semiconductor device formed by an electrochemical method according to a first condition of the present invention. FIGS. 4A and 4B are views showing an electrochemical method according to a second condition of the present invention FIGS. 5A and 5B are views showing a P-type thermoelectric semiconductor element formed by an electrochemical method according to a third condition of the present invention. FIG. 3A, 4A, and 5A show the surface, and FIGS. 3B, 4B, and 5B show cross-sections.

3 to 5, a substrate having a metal electrode formed by stacking Ni / Au on a silicon substrate as a working electrode by sputtering is supported on a liquid electrolyte containing ions for forming a P-type thermoelectric semiconductor device After that, the Pt substrate was used as a counter electrode and the Ag / AgCl was used as a reference electrode, and the electrochemical P-type thermoelectric semiconductor device was electrodeposited.

In this case, a scanning potentiostat (EG and G model 273A) was used to apply a voltage of -0.02 to -0.30V between the working electrode and the counter electrode in the standard three-electrode system to electrodeposit the thermoelectric semiconductor device. Electrodeposition of the electrochemical method was carried out at room temperature.

The composition conditions of the liquid electrolyte are shown in Table 2 below.

division Sb ₂ O ₃ TeO ₂ CTAB Condition 1 0.8mM 2.4mM Condition 2 2.4mM 2.4mM 1 mM Condition 3 4.8 mM 2.4mM 1 mM

That is, in order to form the P-type thermoelectric semiconductor element Sb ₂ Te ₃ , the composition of the liquid electrolyte was changed to be XmM Sb ₂ O ₃ / YmM TeO ₂ (0.8 ≦ X, Y ≦ 4.8), which was dissolved in 1 M HNO ₃ and 33 mM tartaric acid to form a liquid electrolyte.

On the other hand, Condition 2 and Condition 3 further included CTAB (Cetyl Trimethyl Ammonium Bromide) as a surfactant.

3 to 5, the surface of the P-type thermoelectric semiconductor device is rough and the surface of the P-type thermoelectric semiconductor device is not dense under Condition 1, which does not include the surfactant CTAB. However, in Condition 2 and Condition 3 including the surfactant CTAB, The surface roughness of the thermoelectric semiconductor element is reduced, and the cross section becomes dense.

That is, the electrochemical method according to the present invention is carried out at room temperature and under normal pressure, it is possible to maintain mild conditions compared to the high temperature, high pressure process generally proceeds, in addition, in the case of containing a surfactant in the composition of the liquid electrolyte In addition, it can be seen that the surface roughness of the thermoelectric semiconductor device is reduced and the cross section is made compact. Accordingly, the device characteristics of the thermoelectric semiconductor may be improved.

Hereinafter, the device characteristics of the thermoelectric semiconductor when the surfactant is included and when the surfactant is not included will be compared. In order to compare the device characteristics of the thermoelectric semiconductor, a thermoelectric semiconductor as shown in FIG. 1 was manufactured. At this time, the P-type thermoelectric semiconductor device was formed by electrodeposition of an electrochemical method based on the liquid electrolyte of the above- (Bi _0.25 Sb _0.75 ) ₂ Te ₃ , which is an N-type thermoelectric semiconductor device, was formed by electrochemical electrodeposition on the basis of the liquid electrolyte of the following condition 4. That is, a thermoelectric semiconductor as shown in Fig. 1 was produced based on the N-type thermoelectric semiconductor element of Condition 4 and each of the P-type thermoelectric semiconductor elements of Condition 1 to Condition 3.

Condition _{4: 0.2mM Bi (NO 3)} 3 / 0.8mM TeO 2 / 0.8mM Sb 2 O 3 / 1M HNO 3 / 33mM tartaric acid

FIG. 6 is a Seebeck coefficient of a thermoelectric semiconductor including a P-type thermoelectric semiconductor device according to the first to third conditions and an N-type thermoelectric semiconductor device according to a fourth condition, and a power factor thereof according to the present invention. Factor) is a graph showing the change. In this case, the graph X represents the power factor and the graph Y represents the Seebeck coefficient.

Referring to FIG. 6, in the case of the condition 2 and the condition 3 including the CTAB (Cetyl Trimethyl Ammonium Bromide) as the composition of the liquid electrolyte, the Seebeck coefficient and power compared to the condition 1 without the surfactant. It can be seen that the power factor increases. In this case, the power factor corresponds to the performance index considering the change of the electric conductivity and the Seebeck coefficient at the same time.

That is, as described above, in order to improve the thermoelectric performance (performance index: ZT) of the thermoelectric semiconductor material, it is necessary to increase the value of the bekking coefficient (?) Or the electric conductivity (?). The Seebeck coefficient increases and the power factor that simultaneously takes account of the change of the electric conductivity and the Seebeck coefficient increases, thereby improving the performance index of the thermoelectric semiconductor.

On the other hand, in the electrochemical method according to the present invention in Table 1, the Seebeck coefficient of 118 is equivalent to the above condition 1. In the case of Condition 1, the Seebeck coefficient is lower than that of the co- That is, when the liquid electrolyte contains CTAB (Cetyl Trimethyl Ammonium Bromide) as the composition of the liquid electrolyte, the Seebeck coefficient is 250 or more, which means that the Seebeck coefficient is increased as compared with the co-evaporation method which is a general deposition method.

According to the present invention as described above, by electrodepositing the thermoelectric semiconductor element by the electrochemical method, it is possible to prevent damage to the thermoelectric semiconductor element due to high temperature and high pressure.

In addition, by further including a surfactant in the composition of the liquid electrolyte, it is possible to improve the performance index of the thermoelectric semiconductor. On the other hand, CTAB (Cetyl Trimethyl Ammonium Bromide), which is a surfactant, is an example of a cationic surfactant. However, the present invention does not limit the kind of the surfactant. In the present invention, anionic, cationic , And nonionic surfactants may be used.

For example, anionic surfactants include sulfates, sulfonates, phosphates, carboxylic acids, and cationic surfactants include alkylammonium salts, gemini surfactants, cetylethylpiperidinium salts, and dialkyldimethylammoniums. Nonionic surfactants can include primary amines, poly (oxyethylene) oxides, octaethylene glycol monodecyl ethers, octaethylene glycol monohexadecyl ethers.

More specifically, the cationic surfactant may be Catyl Trimethyl Ammonium Bromide (CTAB), the anionic surfactant may be Polyacrylic acid (PAA), and the nonionic surfactant may be Polyoxy ethylene sorbitan monooleate (Tween 80).

In the above description, the surfactant is included in the composition of the liquid electrolyte for forming the P-type thermoelectric semiconductor device. However, the composition of the liquid electrolyte for forming the N-type thermoelectric semiconductor device may include a surfactant, , The composition of the liquid electrolyte for forming the P-type thermoelectric semiconductor device, and the composition of the liquid electrolyte for forming the N-type thermoelectric semiconductor device preferably include a cationic surfactant, CTAB (Cetyl Trimethyl Ammonium Bromide).

For example, in the present invention, the P-type thermoelectric semiconductor device may be Sb ₂ Te ₃ , and the N-type thermoelectric semiconductor device may be Bi ₂ Te ₃ , by including a cationic surfactant in each liquid electrolyte as the surfactant, The surfactant affects the cations Bi ⁺ and Sb ⁺ , thereby reducing the deposition rate of the cations so that they are evenly dispersed, thereby improving the performance index of the thermoelectric semiconductor.

On the other hand, in the present invention, in order to improve the thermoelectric performance (performance index: ZT) of the thermoelectric semiconductor material, Ag, Cu, Pb, Sn and Ge in the composition of the liquid electrolyte for forming a P-type or N-type thermoelectric semiconductor element It may include at least one material selected from the group.

That is, in order to improve the thermoelectric performance (performance index: ZT) of the thermoelectric semiconductor material, the raw material alloy which increases the value of the Seebeck coefficient (α) or the electrical conductivity (σ) or decreases the thermal conductivity (κ) or the specific resistance (ρ). It is preferable to use a material, in which Ag, Cu is used in the composition of the liquid electrolyte for forming a P-type or N-type thermoelectric semiconductor element in order to increase the value of the electrical conductivity σ and to lower the specific resistance ρ. By including at least one material selected from the group consisting of Pb, Sn and Ge, it is possible to improve the electrical properties of the thermoelectric semiconductor device.

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, It will be understood. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

1: thermoelectric module 2: P-type thermoelectric semiconductor device
3: N-type thermoelectric semiconductor device 4: metal electrode

Claims (11)

In the method of manufacturing a thermoelectric semiconductor comprising a thermoelectric semiconductor element,
The thermoelectric semiconductor device is electrodeposited by an electrochemical method,
In the electrochemical method, using the substrate as a working electrode, the substrate is supported on a liquid electrolyte containing ions for forming the thermoelectric semiconductor element, and a constant current or a constant voltage is applied using a counter electrode and a reference electrode. Will be
The liquid electrolyte further comprises a surfactant,
The surfactant includes an anionic surfactant, cationic surfactant or nonionic surfactant,
The cationic surfactant is CTAB (Cetyl Trimethyl Ammonium Bromide) method for producing a thermoelectric semiconductor, characterized in that. The method of claim 1,
Wherein the thermoelectric semiconductor element comprises one or two elements selected from the group consisting of bismuth (Bi) and antimony (Sb) in the 5B group and one or two elements selected from tellurium (Te) and selenium (Se) And a compound represented by the following formula delete The method of claim 1,
Wherein the thermoelectric semiconductor element comprises a P-type thermoelectric semiconductor element and an N-type thermoelectric semiconductor element. delete The method of claim 1,
Wherein the working electrode is a substrate on which a metal electrode having a structure in which Ni / Au is laminated on a silicon substrate by a sputtering method is formed. delete delete The method of claim 1,
Wherein the liquid electrolyte comprises a liquid electrolyte for forming a P-type thermoelectric semiconductor element or a liquid electrolyte for forming an N-type thermoelectric semiconductor element,
Wherein the composition of the liquid electrolyte for forming the P-type thermoelectric semiconductor device and the composition of the liquid electrolyte for forming the N-type thermoelectric semiconductor device include a cationic surfactant. delete The method of claim 1,
The liquid electrolyte further comprises at least one material selected from the group consisting of Ag, Cu, Pb, Sn and Ge.

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