Patent Grant
12010917
The present application is based on PCT/JP2020/024975 filed on Jun. 25, 2020, and claims priority to Japanese Application No. 2019-158254, filed on Aug. 30, 2019, the entire contents of each are incorporated herein by reference.
The present disclosure relates to a thermoelectric conversion material, a thermoelectric conversion element, a thermoelectric conversion module, and an optical sensor.
Ag2Se (silver selenide) used as a thermoelectric conversion material is known (e.g., Non Patent Literature 1).
A thermoelectric conversion material according to the present disclosure is represented by a composition formula Ag2S(1-x)Sex. The value of x is not smaller than 0.2 and not greater than 0.95.
In thermoelectric conversion, heat is directly converted into electric power, so no extra waste is discharged during the conversion. A power generation device utilizing the thermoelectric conversion requires no motor or other drive unit, offering advantages such as easy maintenance of the device.
Efficiency η in converting a temperature difference (heat energy) into electric energy using a material (thermoelectric conversion material) for thermoelectric conversion is given by the following expression (1).
η=ΔT/Th·(M−1)/(M+Tc/Th) (1)
Here, η represents a conversion efficiency, ΔT represents a difference between Th and Tc, Th represents a temperature on the high temperature side, Tc represents a temperature on the low temperature side, M equals to (1+ZT)1/2, ZT=α2ST/κ, ZT represents a dimensionless figure of merit, α represents a Seebeck coefficient, S represents an electrical conductivity, T represents a temperature, and κ represents a thermal conductivity. The conversion efficiency is a monotonically increasing function of ZT. It is important to increase ZT in developing a thermoelectric conversion material. Further, from the standpoint of operating environment, it is desired that a high ZT can be achieved in a low temperature range.
Thus, one of the objects is to provide a thermoelectric conversion material, a thermoelectric conversion element, a thermoelectric conversion module, and an optical sensor which can realize a high ZT in a low temperature range.
According to the thermoelectric conversion material described above, a high ZT can be achieved in a low temperature range.
Firstly, embodiments of the present disclosure will be listed and described. A thermoelectric conversion material according to the present disclosure is represented by a composition formula Ag2S(1-x)Sex. The value of x is not smaller than 0.2 and not greater than 0.95.
The present inventors conducted intensive studies to realize a high ZT in a low temperature range, and have found that with a material represented by a composition formula Ag2S(1-x)Sex where the value of x is not smaller than 0.2 and not greater than 0.95, the value of ZT becomes maximum in a low temperature range. That is, the thermoelectric conversion material represented by the composition formula Ag2S(1-x)Sex where x has a value of not smaller than 0.2 and not greater than 0.95 can realize a high ZT in a low temperature range, for example at a room temperature of about 25° C. As a result, high thermoelectric conversion efficiency can be achieved in the low temperature range.
In the thermoelectric conversion material described above, the value of x may be 0.5 or greater. With this, the maximum value of ZT can be made relatively large in a low temperature range. Accordingly, a higher thermoelectric conversion efficiency can be achieved.
A thermoelectric conversion element of the present disclosure includes: a thermoelectric conversion material portion; a first electrode disposed in contact with the thermoelectric conversion material portion; and a second electrode disposed in contact with the thermoelectric conversion material portion and apart from the first electrode. The thermoelectric conversion material portion is constituted by the above-described thermoelectric conversion material.
In the thermoelectric conversion element of the present disclosure, the material constituting the thermoelectric conversion material portion is the above-described thermoelectric conversion material. Therefore, a high ZT can be achieved in a low temperature range.
A thermoelectric conversion module of the present disclosure includes the above-described thermoelectric conversion element. According to the thermoelectric conversion module of the present disclosure, with the inclusion of the thermoelectric conversion element of the present disclosure capable of realizing a high ZT in a low temperature range, a thermoelectric conversion module that is able to realize a high ZT in a low temperature range can be obtained.
An optical sensor of the present disclosure includes: an absorber that absorbs optical energy; and a thermoelectric conversion material portion connected to the absorber. The thermoelectric conversion material portion is constituted by the above-described thermoelectric conversion material.
In the optical sensor of the present disclosure, the material constituting the thermoelectric conversion material portion is the above-described thermoelectric conversion material. Therefore, an optical sensor that has high sensitivity in a low temperature range can be provided.
Embodiments of the thermoelectric conversion material of the present disclosure will be described below with reference to the drawings. In the drawings referenced below, the same or corresponding parts are denoted by the same reference numerals and the descriptions thereof are not repeated.
A description will be made of a configuration of a thermoelectric conversion material according to Embodiment 1 of the present disclosure. The thermoelectric conversion material according to Embodiment 1 of the present disclosure is represented by a composition formula Ag2S(1-x)Sex. The value of x is not smaller than 0.2 and not greater than 0.95.
The thermoelectric conversion material according to Embodiment 1 can be produced, for example, through the following producing method. Firstly, Ag powder, S powder, and Se powder are prepared. Here, when the thermoelectric conversion material is represented by the composition formula Ag2S(1-x)Sex, the mixing ratios of S and Se are adjusted such that the value of x is not smaller than 0.2 and not greater than 0.95. The powders are mixed, pressed, and solidified into a pellet form, thereby obtaining a green compact. Next, a portion of the obtained green compact in the pellet form is heated for crystallization.
The heating of a portion of the green compact is performed within a chamber having a heater such as a resistance heating wire, for example. The chamber has a reduced pressure. Specifically, the degree of vacuum in the chamber is set to be about 1×10−4 Pa, for example. The green compact is heated with the heater for about one second. When the crystallization start temperature is reached, a portion of the green compact is crystallized. The heating is stopped after the crystallization of the portion of the green compact. In this case, the crystallization is promoted by self-heating without the need of reheating. That is, the remaining portion of the green compact is crystallized by the self-heating of the green compact with the progress of crystallization. In this manner, the thermoelectric conversion material in Embodiment 1 is obtained. Examples of the specific composition of the thermoelectric conversion material include Ag2S0.4Se0.6, with the value of x being 0.6. It should be noted that as the thermoelectric conversion material in the present embodiment, a thermoelectric conversion material of n type is obtained.
Referring to
Accordingly, the thermoelectric conversion material represented by the composition formula Ag2S(1-x)Sex and the value of x is not smaller than 0.2 and not greater than 0.95, as indicated with a region 12A in
Thermoelectric characteristics were measured using a thermoelectric characteristic measuring device (RZ2001i manufactured by Ozawa Science Co., Ltd.) The way of measuring the thermoelectric characteristics is as follows. Firstly, with a thermoelectric conversion material being fixed bridged between a pair of quartz fixtures, the atmosphere is heated using a resistive heating furnace. One of the quartz fixtures is made hollow to let nitrogen gas flow therein for cooling, thereby cooling one end portion of the thermoelectric conversion material. This gives a temperature difference to the thermoelectric conversion material. In the thermoelectric conversion material, a temperature difference between two points on a surface of the thermoelectric conversion material is measured using a platinum-platinum rhodium thermocouple (type R thermocouple). A voltmeter is connected to the thermocouple to measure a voltage generated due to the temperature difference between the two points. This makes it possible to measure the generated voltage with respect to the temperature difference, and on the basis of this to estimate a Seebeck coefficient of the material. A resistance value is measured in accordance with a four-terminal method. Specifically, two electric wires are connected on the outer side relative to two platinum wires to which the voltmeter is connected. Then, a current is passed through the electric wires and the amount of voltage drop is measured using the voltmeter located on the inner side. In this manner, the resistance value of the thermoelectric conversion material is measured in accordance with the four-terminal method. The resistivity is derived from the resistance value measured. It should be noted that the reciprocal of the resistivity thus derived is the electrical conductivity. Further, the thermal conductivity κ was measured using a laser flash method, using a measuring device (model number: LFA 457) manufactured by NETZSCH-Geraetebau GmbH. The Seebeck coefficient was calculated by plotting the measured temperature differences and the generated voltages on a graph and deriving the slope of the graph.
In the thermoelectric conversion material described above, the value of x may be 0.5 or greater. With this, the maximum value of ZT can be made relatively large in a low temperature range. Specifically, the value of x is set to be 0.5 or greater and 0.95 or smaller, as indicated with a region 12B in
As for the low temperature range, if the temperature at which ZT shows a maximum value is desired to be 100° C. or lower, the value of x may be set to be 0.2 or greater and 0.9 or smaller, as indicated with a region 12C in
A description will now be made of a power generation element as an embodiment of a thermoelectric conversion element using the thermoelectric conversion material according to the present disclosure.
The p type thermoelectric conversion material portion 22 is constituted of a thermoelectric conversion material having p type conductivity. The thermoelectric conversion material constituting the n type thermoelectric conversion material portion 23 is the thermoelectric conversion material of Embodiment 1.
The p type thermoelectric conversion material portion 22 and the n type thermoelectric conversion material portion 23 are disposed side by side with a spacing therebetween. The high temperature side electrode 24 is disposed to extend from one end 31 of the p type thermoelectric conversion material portion 22 to one end 32 of the n type thermoelectric conversion material portion 23. The high temperature side electrode 24 is disposed so as to contact both the one end 31 of the p type thermoelectric conversion material portion 22 and the one end 32 of the n type thermoelectric conversion material portion 23. The high temperature side electrode 24 is disposed to connect the one end 31 of the p type thermoelectric conversion material portion 22 and the one end 32 of the n type thermoelectric conversion material portion 23. The high temperature side electrode 24 is composed of an electrically conductive material, such as a metal. The high temperature side electrode 24 is in ohmic contact with the p type thermoelectric conversion material portion 22 and the n type thermoelectric conversion material portion 23.
The first low temperature side electrode 25 is disposed in contact with another end 33 of the p type thermoelectric conversion material portion 22. The first low temperature side electrode 25 is disposed apart from the high temperature side electrode 24. The first low temperature side electrode 25 is composed of an electrically conductive material, such as a metal. The first low temperature side electrode 25 is in ohmic contact with the p type thermoelectric conversion material portion 22.
The second low temperature side electrode 26 is disposed in contact with another end 34 of the n type thermoelectric conversion material portion 23. The second low temperature side electrode 26 is disposed apart from the high temperature side electrode 24 and the first low temperature side electrode 25. The second low temperature side electrode 26 is composed of an electrically conductive material, such as a metal. The second low temperature side electrode 26 is in ohmic contact with the n type thermoelectric conversion material portion 23.
The wire 27 is composed of an electric conductor such as a metal. The wire 27 electrically connects the first low temperature side electrode 25 and the second low temperature side electrode 26.
In the π type thermoelectric conversion element 21, when a temperature difference is formed so that the one end 31 side of the p type thermoelectric conversion material portion 22 and the one end 32 side of the n type thermoelectric conversion material portion 23 are at a high temperature and the other end 33 side of the p type thermoelectric conversion material portion 22 and the other end 34 side of the n type thermoelectric conversion material portion 23 are at a low temperature, for example, then p type carriers (holes) move from the one end 31 side toward the other end 33 side in the p type thermoelectric conversion material portion 22. At this time, in the n type thermoelectric conversion material portion 23, n type carriers (electrons) move from the one end 32 side toward the other end 34 side. As a result, a current flows through the wire 27 in the direction of the arrow I. In this manner, power generation by thermoelectric conversion using a temperature difference is achieved in the π type thermoelectric conversion element 21. In other words, the π type thermoelectric conversion element 21 is a power generation element.
As the material constituting then type thermoelectric conversion material portion 23, the thermoelectric conversion material of Embodiment 1 capable of realizing a high ZT in a low temperature range, for example, is adopted. As a result, the π type thermoelectric conversion element 21 is a power generation element that is highly efficient in a low temperature range.
In the above embodiment, the π type thermoelectric conversion element has been described as an example of the thermoelectric conversion element of the present disclosure. However, the thermoelectric conversion element of the present disclosure is not limited thereto. The thermoelectric conversion element of the present disclosure may be a thermoelectric conversion element having another structure, such as an I type (unileg) thermoelectric conversion element, for example.
A plurality of π type thermoelectric conversion elements 21 can be electrically connected to obtain a power generation module as a thermoelectric conversion module. A power generation module 41, the thermoelectric conversion module of the present embodiment, has a structure of a plurality of π type thermoelectric conversion elements 21 connected in series.
The low temperature side insulator substrate 28 is disposed on a main surface side of the plate-shaped low temperature side electrodes 25, 26 opposite to the side on which they contact the p type thermoelectric conversion material portions 22 and the n type thermoelectric conversion material portions 23. One low temperature side insulator substrate 28 is disposed for the plurality of (all the) low temperature side electrodes 25, 26. The high temperature side insulator substrate 29 is disposed on a side of the plate-shaped high temperature side electrodes 24 opposite to the side on which they contact the p type thermoelectric conversion material portions 22 and the n type thermoelectric conversion material portions 23. One high temperature side insulator substrate 29 is disposed for the plurality of (all the) high temperature side electrodes 24.
Wires 27 are connected to the high temperature side electrodes 24 or the low temperature side electrodes 25, 26 in contact with the p type thermoelectric conversion material portion 22 or the n type thermoelectric conversion material portion 23 located at respective ends of the series-connected p type thermoelectric conversion material portions 22 and n type thermoelectric conversion material portions 23. When a temperature difference is formed so that the high temperature side insulator substrate 29 side attains a high temperature and the low temperature side insulator substrate 28 side attains a low temperature, then the series-connected p type thermoelectric conversion material portions 22 and n type thermoelectric conversion material portions 23 permit a current to flow in the directions of the arrows I, as in the case of the π type thermoelectric conversion element 21 described above. In this manner, power generation by thermoelectric conversion using a temperature difference is achieved in the power generation module 41.
A description will now be made of an infrared sensor, which is an optical sensor, as another embodiment of the thermoelectric conversion element using the thermoelectric conversion material according to the present disclosure.
The infrared sensor 51 includes the substrate 54, an etching stop layer 55, an n type thermoelectric conversion material layer 56, an n+ type ohmic contact layer 57, an insulator layer 58, a p type thermoelectric conversion material layer 59, n side ohmic contact electrodes 61, p side ohmic contact electrodes 62, a heat absorption pad 63, an absorber 64, and a protective film 65.
The substrate 54 is composed of an insulator such as silicon dioxide. The substrate 54 has a recess 66 formed therein. The etching stop layer 55 is formed to cover a surface of the substrate 54. The etching stop layer 55 is composed of an insulator such as silicon nitride, for example. A gap is formed between the etching stop layer 55 and the recess 66 of the substrate 54.
The n type thermoelectric conversion material layer 56 is formed on a main surface of the etching stop layer 55 opposite to the substrate 54. The thermoelectric conversion material constituting the n type thermoelectric conversion material layer 56 is the thermoelectric conversion material of Embodiment 1. The n+ type ohmic contact layer 57 is formed on a main surface of the n type thermoelectric conversion material layer 56 opposite to the etching stop layer 55. The n+ type ohmic contact layer 57 is doped with n type impurities that cause the generation of n type carriers (electrons) as majority carriers, for example, whereby the n+ type ohmic contact layer 57 has n type conductivity.
The n side ohmic contact electrode 61 is disposed to contact a central portion of a main surface of the n+ type ohmic contact layer 57 opposite to the n type thermoelectric conversion material layer 56. The n side ohmic contact electrode 61 is composed of a material that can make ohmic contact with the n+ type ohmic contact layer 57, such as a metal. The insulator layer 58, composed of an insulator such as silicon dioxide, for example, is disposed on the main surface of the n+ type ohmic contact layer 57 opposite to the n type thermoelectric conversion material layer 56. The insulator layer 58 is disposed on the main surface of the n+ type ohmic contact layer 57 on the p type thermoelectric conversion material portion 52 side with respect to the n side ohmic contact electrode 61.
The protective film 65 is also disposed on the main surface of the n+ type ohmic contact layer 57 opposite to the n type thermoelectric conversion material layer 56. The protective film 65 is disposed on the main surface of the n+ type ohmic contact layer 57 on the opposite side from the p type thermoelectric conversion material portion 52 side with respect to the n side ohmic contact electrode 61. On the main surface of the n+ type ohmic contact layer 57 opposite to the n type thermoelectric conversion material layer 56, another n side ohmic contact electrode 61 is disposed on the opposite side from the above-described n side ohmic contact electrode 61, with the protective film 65 sandwiched therebetween.
The p type thermoelectric conversion material layer 59 is disposed on a main surface of the insulator layer 58 opposite to the n+ type ohmic contact layer 57.
The protective film 65 is disposed at a central portion on a main surface of the p type thermoelectric conversion material layer 59 opposite to the insulator layer 58. On the main surface of the p type thermoelectric conversion material layer 59 opposite to the insulator layer 58, a pair of p side ohmic contact electrodes 62 are disposed sandwiching the protective film 65 therebetween. The p side ohmic contact electrodes 62 are composed of a material that can make ohmic contact with the p type thermoelectric conversion material layer 59, such as a metal. Of the pair of p side ohmic contact electrodes 62, the p side ohmic contact electrode 62 on the n type thermoelectric conversion material portion 53 side is connected to the n side ohmic contact electrode 61.
The absorber 64 is disposed to cover main surfaces of the mutually connected p side ohmic contact electrode 62 and n side ohmic contact electrode 61 opposite to the n+ type ohmic contact layer 57. The absorber 64 is composed of titanium, for example. The heat absorption pad 63 is disposed to be in contact with the top surface of the p side ohmic contact electrode 62 that is not connected to the n side ohmic contact electrode 61. The heat absorption pad 63 is also disposed to be in contact with the top surface of the n side ohmic contact electrode 61 that is not connected to the p side ohmic contact electrode 62. As a material constituting the heat absorption pad 63, gold (Au)/titanium (Ti), for example, is adopted. That is, the absorber 64 and the n type thermoelectric conversion material layer 56 are thermally connected to each other. The absorber 64 and the p type thermoelectric conversion material layer 59 are thermally connected to each other.
When the infrared sensor 51 is irradiated with infrared rays, the absorber 64 absorbs the energy of the infrared rays. As a result, the temperature of the absorber 64 rises. On the other hand, the temperature rise of the heat absorption pad 63 is suppressed. This forms a temperature difference between the absorber 64 and the heat absorption pad 63. Accordingly, in the p type thermoelectric conversion material layer 59, p type carriers (holes) move from the absorber 64 side toward the heat absorption pad 63 side. On the other hand, in the n type thermoelectric conversion material layer 56, n type carriers (electrons) move from the absorber 64 side toward the heat absorption pad 63 side. Then, by extracting a current generated as a result of the migration of the carriers from the n side ohmic contact electrodes 61 and the p side ohmic contact electrodes 62, the infrared rays are detected.
In the infrared sensor 51 of the present embodiment, the thermoelectric conversion material of Embodiment 1 is adopted as the thermoelectric conversion material constituting the n type thermoelectric conversion material layer 56. As a result, the infrared sensor 51 is an infrared sensor that is highly sensitive in a low temperature range.
It should be understood that the embodiments disclosed herein are illustrative and non-restrictive in every respect. The scope of the present disclosure is defined by the terms of the claims, rather than the description above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2019-158254 | Aug 2019 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2020/024975 | 6/25/2020 | WO |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2021/039081 | 3/4/2021 | WO | A |
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