KR20100091333A - Porous organic thermoelectric device - Google Patents
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- H—ELECTRICITY
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- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/856—Thermoelectric active materials comprising organic compositions
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
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Abstract
Description
본 발명은 다공성 유기박막을 갖는 유기열전소자 및 이의 제조방법에 관한 것이다. The present invention relates to an organic thermoelectric device having a porous organic thin film and a method of manufacturing the same.
열전현상은 두 물질 사이에 전류를 인가함으로써 재료 (thermoelectric material) 접합부 양단에 발열 및 냉각이 이루어지거나 역으로 두 물질간의 온도차에 의해 기전력이 발생하는 현상으로, 열전소자는 열을 전기로 또는 전기를 열로 직접 변환시키는 기능을 갖는 금속 또는 세라믹 소자를 말한다. 이러한 열전소자는 쓰레기 소각에 의한 폐열, 터빈발전 폐열, 자동차 배기가스의 열, 도시가스의 연소 배열 및 산업폐열 등을 사용하여 열전발전 또는 열전냉각 등 여러 분야에 응용되고 있다. Thermoelectric phenomenon is a phenomenon in which electromotive force is generated by heat generation and cooling across a thermoelectric material junction by applying a current between two materials or vice versa by a temperature difference between two materials. It refers to a metal or ceramic device having a function of directly converting to heat. Such thermoelectric devices have been applied to various fields such as thermoelectric power generation or thermoelectric cooling by using waste heat from incineration of waste, waste heat from turbine power generation, heat from automobile exhaust gas, combustion arrangement of city gas, and industrial waste heat.
1950년대 Bi-Te계 열전소재가 개발된 이후 열전재료의 에너지 변환효율을 나타내는 열전 성능지수는 상온에서 1 이하의 값을 보여 왔으며 이를 통하여 얻을 수 있는 최대 냉각효율은 약 8%로 다양한 전자기기에의 사용이 제한적이었으나, 2000 년대에 접어들어 초격자 구조 혹은 양자 구속효과 등 나노 소재 및 공정 기술이 접목된 결과로 열전 성능지수는 획기적인 개선을 보이고 있으며 현재까지 최고 2.4의 열전 성능 지수 값을 갖는 소자를 보고하고 있다. 또한, 재료 내에서 열전달을 담당하는 포논(Phonon) 의 파장과 전기전달을 담당하는 전자 (혹은 정공)의 평균 자유행로로부터 열전 재료를 이 특성 파장에 상응하는 길이 단위를 지닌 나노구조로 제조함으로 전자 에너지 준위 밀도를 제어하여 비교적 큰 값의 상수 및 전도도를 얻어 열전성능지수 Seeback 값을 향상시키거나, 열전달을 담당하는 포논을 산란시켜 열전도도를 억제함과 동시에 에너지 밴드갭 조절을 통하여 전기적 전도도는 그대로 유지하는 방식으로 열전 성능 지수를 획기적으로 개선하고 있다. Since the development of Bi-Te-based thermoelectric materials in the 1950's, the thermoelectric performance index, which represents the energy conversion efficiency of thermoelectric materials, has been shown to be less than 1 at room temperature. Although the use of is limited, the thermoelectric performance index has improved dramatically as a result of incorporating nanomaterials and process technologies such as superlattice structure or quantum confinement effect into the 2000s. Is reporting. In addition, from the average free path of the wavelength of the phonon responsible for heat transfer and the electrons (or holes) responsible for heat transfer, the thermoelectric material is manufactured into nanostructures with length units corresponding to this characteristic wavelength. Control the energy level density to obtain a relatively large value of constant and conductivity to improve the thermal performance index Seeback value, or scatter the phonons responsible for heat transfer to suppress thermal conductivity and control the energy band gap, while maintaining electrical conductivity as it is. By maintaining it, the thermoelectric performance index is dramatically improved.
이와 같이 종래 기술의 펠티에 효과가 있는 열전물질들은 다양한 종류가 개발되었으며, 그 종류들은 Bi2Te3, Sb2Te3, Bi2Se3, CsBi4Te6, PbTe, PbS, PbSe, Zn4Sb3, 등의 계통과, skutterudite 계통과, LaFeSb 계통과, LaCo206 계통과, 그리고 Bi, Sb, B, Si, Ge, Te, Se, Ga, In 등의 단독원소들과 같은 열전물질들이 있다. 그리고 종래 기술은 열전소자 혹은 열전장치로 만들기 위하여, 상기의 다양한 종류의 열전물질들을 펠리트, 다층펠리트, 선, 박막. 다층박막, 세그먼트, 초격자구조, 열전 장치, 등의 다양한 형태로 만들고 있다. As described above, various types of thermoelectric materials having a Peltier effect of the prior art have been developed, and the types are Bi 2 Te 3 , Sb 2 Te 3 , Bi 2 Se 3 , CsBi 4 Te 6 , PbTe, PbS, PbSe, and Zn 4 Sb. 3, the grid and, skutterudite system and, LaFeSb system and, LaCo 2 0 6 grid with, and thermal materials, such as single elements such as Bi, Sb, B, Si, Ge, Te, Se, Ga, in, such that have. In the prior art, the various types of thermoelectric materials may be formed into pellets, multilayer pellets, wires, and thin films in order to make a thermoelectric device or a thermoelectric device. It is made in various forms such as multilayer thin film, segment, superlattice structure, thermoelectric device, etc.
상기 열전소개의 특성은 통상적으로 하기 식으로 표현되는 성능지수(Z)로 평가할 수 있는바, 성능지수가 크면 클수록 발생되는 전위차가 커지므로 우수한 특성 을 나타낸다. The characteristics of the thermoelectric introduction can be generally evaluated by the performance index (Z) represented by the following formula, the larger the performance index shows an excellent characteristic because the potential difference is greater.
ＺＴ＝(Ｓ2σ/κ)ＴVT = (S 2 σ / κ)
(S: 제벡(Seebeck)계수, σ : 전기전도도, κ : 열전도도, T : 온도)(S: Seebeck coefficient, σ: electrical conductivity, κ: thermal conductivity, T: temperature)
따라서 상기 식으로부터 열전소재의 응용을 위해서는 제벡계수 및 전기전도도가 크고 열전도도가 작은 소재가 바람직하며, 이는 소재의 형상 및 기공도, 캐리어(carrier) 농도, 결정구조, 결합의 성질, 결합강도 등에 따라 최적화가 가능하다. 특히 열전소자에 있어서 열전소자의 성능은 열전도도와 반비례한다. 그 이유는, 열전도도를 낮춘다면 열전소자 양단의 온도차가 더욱 커지고, 양 단의 온도차가 커질수록 열전소자의 성능이 향상되기 때문이다. 그러나, 종래 열전물질의 열효율이 보통 10％, 최고 24％에 불과하며, 냉매압축기화형의 열효율 40％ 보다 작다. 그러므로 종래기술은 에너지 소모가 많고, 비경제적이므로, 냉각장치와 발전장치로 많이 사용되지 못하는 문제점이 있다. 이와 같이 종래기술의 열효율이 낮은 가장 큰 원인은 열전물질의 격자열전도도와 캐리어의 열전도도가 높아서 열전도로 인하여 다량의 열이 누설되기 때문이다. Therefore, for the application of the thermoelectric material from the above formula, the Seebeck coefficient and the material having high electrical conductivity and low thermal conductivity are preferable, which is the shape and porosity of the material, carrier concentration, crystal structure, bonding properties, bonding strength, etc. It is possible to optimize accordingly. In particular, in thermoelectric devices, the performance of thermoelectric devices is inversely proportional to the thermal conductivity. The reason is that if the thermal conductivity is lowered, the temperature difference across the thermoelectric element becomes larger, and as the temperature difference between both ends increases, the performance of the thermoelectric element is improved. However, the thermal efficiency of the conventional thermoelectric material is usually only 10%, at most 24%, and is less than the thermal efficiency of the refrigerant compression type type 40%. Therefore, the conventional technology is energy-consuming and uneconomical, there is a problem that can not be used a lot as a cooling device and a power generation device. The biggest reason for the low thermal efficiency of the prior art is that a large amount of heat leaks due to thermal conductivity because the lattice thermal conductivity of the thermoelectric material and the thermal conductivity of the carrier are high.
한편, 일반적으로 공기는 열전도도가 매우 낮은바, 열전소자 내부에 다수의 기공이 포함될수록 열전소자의 성능은 향상될 수 있다. 따라서 다공성 열전소자가 필요하고, 강도를 유지하면서 최대한 많은 수의 기공을 확보할 필요가 있다. 기공형성제 및 결합제의 첨가에 의한 다공성 무기열전소자에 대해서는 특허등록 제10-0805726호에서 개시한 바 있으나, 무기 열전소자의 경우 원자재의 값이 비싸고 그 효율이 많이 개선되지 않고, 열전모듈 제작 공정이 복잡한 단점이 있다. On the other hand, in general, air has a very low thermal conductivity, and as the number of pores is included in the thermoelectric element, the performance of the thermoelectric element may be improved. Therefore, a porous thermoelectric element is required, and it is necessary to secure as many pores as possible while maintaining strength. Porous inorganic thermoelectric elements by the addition of pore-forming agents and binders have been disclosed in Patent Registration No. 10-0805726. However, in the case of inorganic thermoelectric elements, raw materials are expensive and their efficiency is not improved much. This is a complex disadvantage.
또한, 박막형 열전소재는 초격자 등의 나노 구조체 형성 등을 통하여 덩어리 형태의 열전소재에 비해 그 성능을 획기적으로 높일 수 있을 뿐만 아니라 열전 소자 제작시 냉각밀도가 높아 국부적인 냉각을 필요로 하는 곳이나 첨단 전자소자의 온도 제어 등에 널리 이용될 수 있다. In addition, the thin-film thermoelectric material can significantly increase its performance compared to agglomerate thermoelectric material by forming nanostructures such as super lattice, and also requires local cooling due to high cooling density when manufacturing thermoelectric elements. It can be widely used for temperature control of advanced electronic devices.
특히, 상온 근방에서 우수한 열전 특성을 보이는 물질로는 Bi2Te3 등과 같은 비스무스 텔루라이드계 합금을 예로 들 수 있는데, 현재 상용화되고 있는 대부분의 열전모듈은 Bi2Te3 합금에 안티몬(Sb)을 첨가하여 p-형 열전반도체를 제조하고 셀레늄(Se)을 첨가하여 n-형 열전반도체를 제조한 후 p-n 접합 어레이 형태로 만들어 제조하고 있다. 구체적으로는, 미국특허 제 5,318,743 호에 개시된 바와 같이, 분말야금 등의 방법을 이용하여 덩어리 형태의 p-형 및 n-형 소재를 제조한 후 이들을 잘게 썰어 p-n 접합 어레이를 형성하여 열전모듈을 제작하고 있다.Particularly, examples of materials exhibiting excellent thermoelectric properties at room temperature include bismuth telluride-based alloys such as Bi 2 Te 3. Most of the thermoelectric modules currently commercialized include antimony (Sb) in Bi 2 Te 3 alloys. P-type thermoconductors are prepared by adding and selenium (Se) is added to prepare n-type thermoconductors, and then pn junction arrays are manufactured. Specifically, as disclosed in U.S. Patent No. 5,318,743, p-type and n-type materials in the form of agglomerates are manufactured by using powder metallurgy, etc., and then, finely sliced to form a pn junction array to fabricate a thermoelectric module. Doing.
박막형 열전소재로부터 소자를 제작하기 위해서는, 절연성 기판 위에 전극용 금속 박막을 먼저 증착하고 이를 패터닝한 후 형성된 금속전극 위에 열전소재 박막을 증착하는 공정을 수행하여야 한다. 그러나, 금속물질과 열전소재 물질간의 격자 부정합, 화학적 비친화성 등으로 인해 성장되는 박막의 전기적 특성 및 열전 특성 등이 크게 저하될 뿐만 아니라 전극용 금속층과의 접착력 및 박막의 표면형상 등이 크게 떨어지는 문제가 발생한다. 상기 문제를 해결하기 위해, 예를 들면 전극용 금 속 박막 위에 열증착 등의 방법으로 열전소재 박막을 증착시킬 경우, 열전소재 박막 증착 후 열처리 공정을 수행하여 그 특성을 개선시키고 있으나, 박막 증착 후 열처리하는 상기 방법은 공정상 번거로울 뿐만 아니라 장시간 소요되고 수율이 낮은 등의 문제점이 있다.In order to fabricate a device from a thin film thermoelectric material, a process of depositing a metal thin film for an electrode on an insulating substrate and patterning the first thin film is followed by depositing a thermoelectric thin film on the formed metal electrode. However, due to lattice mismatch between the metal material and the thermoelectric material and chemical incompatibility, the electrical and thermoelectric properties of the grown thin film are greatly reduced, and the adhesion to the metal layer for the electrode and the surface shape of the thin film are greatly reduced. Occurs. In order to solve the above problem, for example, when depositing a thermoelectric material thin film on the metal thin film for electrodes by a method such as thermal evaporation, the characteristics of the heat treatment after the deposition of the thermoelectric material thin film is improved, but after the thin film deposition The method of heat treatment is not only troublesome in process, but also takes a long time and has a low yield.
이에 본 발명자는 박막형 열전소자를 제조함에 있어서 상기와 같은 문제점을 해결하면서도 기존의 무기물보다 원자재 값이 저렴하고 열전 모듈 제작공정이 간단하고 대면적화가 용이하도록 하기 위하여, 전극이 코팅된 절연기판에 발포제 및 유기물의 혼합유기용액을 도포하고 발포시킴으로써 박막형 다공성 유기열전소자를 제조함으로써 본 발명을 완성하기에 이르렀다. In order to solve the above problems in manufacturing a thin-film thermoelectric device, the present inventors have lower raw materials than conventional inorganic materials, and the process of fabricating a thermoelectric module is simple and facilitates large area. The present invention has been completed by producing a thin-film porous organic thermoelectric device by coating and foaming a mixed organic solution of an organic material.
따라서 본 발명은 박막형 다공성 유기열전소자 및 이의 제조방법을 제공하고자 한다. Accordingly, the present invention is to provide a thin-film porous organic thermoelectric device and a method of manufacturing the same.
본 발명은 다공성 유기활성층을 형성하여 열전도도를 감소시키고 전자 및 정공도를 항샹시켜 열전효율을 높인 다공성 유기열전소자 및 이의 제조방법에 관한 것이다. 보다 구체적으로 본 발명은 온도차에 의해 전류를 발생시키는 활성층이 나노 또는 마이크로 크기의 구멍(Pore)이 형성된 유기박막으로 구성되도록 한 다공성 유기열전소자에 관한 것이다. 또한 본 발명은 발포제(foaming agent) 또는 포로젠(porogen)을 이용하여 나노 또는 마이크로 크기의 다공성 유기활성층을 형성하도록 하는 다공성 유기열전소자의 제조방법에 관한 것이다. The present invention relates to a porous organic thermoelectric device and a method for manufacturing the same, forming a porous organic active layer to reduce the thermal conductivity and enhance the thermoelectric efficiency by enhancing the electron and hole conductivity. More specifically, the present invention relates to a porous organic thermoelectric device in which an active layer that generates a current due to a temperature difference is composed of an organic thin film in which nano- or micro-sized pores are formed. The present invention also relates to a method of manufacturing a porous organic thermoelectric device for forming a porous organic active layer of nano or micro size using a foaming agent or porogen.
이하, 본 발명을 자세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명의 제 1 견지에 의하면, 본 발명은 절연성 기판(유리, 금속 플라스틱) 과, 상기 기판 위에 형성된 하부전극과, 상기 하부전극 위에 코팅된 박막과, 상기 박막 위에 형성된 상부전극으로 구성된 열전소자에 있어서, 상기 박막은 나노 또는 마이크로 크기의 다공을 가지는 유기박막인 것을 특징으로 하는 다공성 유기열전소자에 관한 것이다. 본 발명의 상기 유기박막은 전자 및 정공이 생성되어 흐를 수 있는 고분자 또는 고분자와 단분자, 금속, 무기입자 등의 혼합박막이 모두 가능하다. 상부전극 및 하부전극 사이의 열차이(Thermal Difference)이에 의해서 유기열전소자의 유기활성층에 전자(electron)와 정공(hole)이 생긴 후 이동하여 전기에너지를 발생시키므로 열전도를 억제시키고 전하이동도를 향상시켜 소자의 열전효율을 높일 수 있다. 상기 다공성 유기박막의 두께는 직경이 10㎚ ~ 100㎛ 이 바람직하며. 상기 다공성 유기박막은 전하이동도를 높이기 위하여 정공운반물질과 전자운반물질을 단독 또는 혼합하여 포함할 수 있다. According to a first aspect of the present invention, the present invention provides a thermoelectric device comprising an insulating substrate (glass, metal plastic), a lower electrode formed on the substrate, a thin film coated on the lower electrode, and an upper electrode formed on the thin film. In the above, the thin film relates to a porous organic thermoelectric device, characterized in that the organic thin film having a nano- or micro-sized pores. The organic thin film of the present invention may be a mixed thin film of a polymer or a polymer capable of generating electrons and holes and flowing with a single molecule, a metal, an inorganic particle, and the like. The thermal difference between the upper electrode and the lower electrode causes electrons and holes to form in the organic active layer of the organic thermoelectric element and then moves to generate electrical energy, thereby suppressing thermal conductivity and improving charge mobility. The thermoelectric efficiency of the device can be improved. The thickness of the porous organic thin film is preferably 10nm ~ 100㎛ diameter. The porous organic thin film may include a hole transport material and an electron transport material alone or mixed to increase the charge mobility.
또한 바람직하게는 상기 하부전극은 투명전극(ITO), 하이브리드 형 Bi2Te3, Sb2Te3, Bi2Se3, CsBi4Te6, PbTe, PbS, PbSe, Zn4Sb3 계 물질, skutterudite 계 물질, LaFeSb 계 물질, LaCo206 계 물질 및 Al, Ag, Au, Cu, Bi, Sb, B, Si, Ge, Te, Se, Ga, In 으로 구성되는 단독원소 중에서 선택되는 어느 하나일 수 있다. 본 발명의 일 실시예에서는 전기전도도가 높고 광학적으로 투명도가 높은 인듐 주석 산화물 (Indium tin oxide)로 코팅된 유리 기판에 유기박막을 형성시켜 다공성 유기열전소자를 제조하였다. Also preferably, the lower electrode may be a transparent electrode (ITO), a hybrid type Bi 2 Te 3 , Sb 2 Te 3 , Bi 2 Se 3 , CsBi 4 Te 6 , PbTe, PbS, PbSe, Zn 4 Sb 3 based material, skutterudite At least one selected from a group material, a LaFeSb material, a LaCo 2 O 6 material, and a single element consisting of Al, Ag, Au, Cu, Bi, Sb, B, Si, Ge, Te, Se, Ga, In Can be. In an embodiment of the present invention, a porous organic thermoelectric device was manufactured by forming an organic thin film on a glass substrate coated with indium tin oxide having high electrical conductivity and high optical transparency.
또한 바람직하게는 상기 정공운반물질은 poly(3-hexylthiophene) (P3HT), poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylene vinylene] (MDMO-PPV) 등이 선택될 수 있다. 본 발명의 일 실시예에서는 정공운반층으로써 P3HT를 사용하였다. 또한, 전자운반물질은 ZnO 나노입자, TiO2 나노입자, poly(9,9-dioctylfluorene-alt-benzothiadiazole) (F8BT) 및 1-(3-methoxycarbonyl)-propyl-1-phenyl-(6,6)C61 (PCBM) 등에서 선택될 수 있다. Also preferably, the hole transport material may be poly (3-hexylthiophene) (P3HT), poly [2-methoxy-5- (3 ', 7'-dimethyloctyloxy) -1,4-phenylene vinylene] (MDMO-PPV), or the like. Can be selected. In one embodiment of the present invention, P3HT was used as the hole transport layer. In addition, electron transporting materials include ZnO nanoparticles, TiO 2 nanoparticles, poly (9,9-dioctylfluorene-alt-benzothiadiazole) (F8BT) and 1- (3-methoxycarbonyl) -propyl-1-phenyl- (6,6) C 61 (PCBM) and the like.
본 발명의 다공성 유기열전소자를 제조함에 있어서, 구멍 또는 기공을 형성시키는 다양한 방법 중에서 특히 발포제(foaming agent) 또는 포로젠(porogen)을 이용하였다. 즉 본 발명에서는 유기물과 발포제(Foaming agent) 또는 포로젠(porogen)을 혼합한 용액을 전극 기판 위에 도포하고, 그 기판을 일정 온도 이상 올려주어 발포제(Foaming agent)가 발포하는 성질을 이용하여 유기물 내에 나노 또는 마이크로 크기의 다공(pores)을 만들어 줌으로써, 열전도도를 줄이고 열전 효율을 높인 다공성 유기열전소자를 제조하였다.In manufacturing the porous organic thermoelectric device of the present invention, among various methods of forming pores or pores, a foaming agent or a porogen was used. That is, in the present invention, a solution in which an organic material and a foaming agent or a porogen are mixed is coated on an electrode substrate, and the substrate is raised above a predetermined temperature to foam the foaming agent in the organic material. By making pores of nano or micro size, a porous organic thermoelectric device having reduced thermal conductivity and improved thermoelectric efficiency was manufactured.
따라서 본 발명의 제 2견지에 의하면, 본 발명은 절연성 기판과, 상기 기판 위에 형성된 하부전극과, 상기 하부전극 위에 코팅된 박막과, 상기 박막 위에 형성된 상부전극으로 구성된 열전소자를 제조하는 방법에 있어서, 상기 박막의 코팅은 상기 하부전극 위에 유기물과 발포제가 포함된 혼합유기용액을 도포하고; 용매를 증발시킨 후; 발포제를 발포시켜 나노 또는 마이크로 크기의 다공을 가지는 유기활성층을 형성함에 의하여 이루어지는 것을 특징으로 하는 다공성 유기열전소자의 제조방법을 제공한다. Accordingly, according to a second aspect of the present invention, the present invention provides a method for manufacturing a thermoelectric element comprising an insulating substrate, a lower electrode formed on the substrate, a thin film coated on the lower electrode, and an upper electrode formed on the thin film. The coating of the thin film is to apply a mixed organic solution containing an organic material and a blowing agent on the lower electrode; After evaporating the solvent; It provides a method for producing a porous organic thermoelectric device characterized in that the foaming agent is formed by forming an organic active layer having nano or micro sized pores.
이 때 상기 혼합유기용액의 도포는 10㎚ ~ 100㎛의 두께로 도포하고, 상기 혼합유기용액의 용매를 40 ~ 60 ℃에서 10 ~ 20 분간 증발시킨 다음, 120 ~ 160 ℃에서 발포시키는 것이 바람직하다. At this time, the application of the mixed organic solution is applied to a thickness of 10nm ~ 100㎛, evaporate the solvent of the mixed organic solution for 10 to 20 minutes at 40 ~ 60 ℃, it is preferable to foam at 120 ~ 160 ℃. .
또한 바람직하게는 상기 유기활성층은 정공운반물질 또는 전자운반물질을 단독 또는 혼합하여 포함할 수 있으며, 상기 정공운반물질로는 poly(3-hexylthiophene) (P3HT), poly[2-methoxy-5-(3',7'-dimethyloctyl oxy)-1,4-phenylenevinylene] (MDMO-PPV) 등이 선택될 수 있다. 본 발명의 일 실시예에서는 정공운반층으로써 P3HT를 사용하였다. 또한, 전자운반물질은 ZnO 나노입자, TiO2 나노입자, poly(9,9-dioctylfluorene-alt -benzothiadiazole) (F8BT) 및 1-(3-methoxycarbonyl)-propyl-1- phenyl-(6,6)C61 (PCBM) 등에서 선택될 수 있다. Also preferably, the organic active layer may include a hole transporting material or an electron transporting material alone or in a mixture. The hole transporting material may be poly (3-hexylthiophene) (P3HT), poly [2-methoxy-5- ( 3 ', 7'-dimethyloctyl oxy) -1,4-phenylenevinylene] (MDMO-PPV) and the like can be selected. In one embodiment of the present invention, P3HT was used as the hole transport layer. In addition, electron transporting materials include ZnO nanoparticles, TiO 2 nanoparticles, poly (9,9-dioctylfluorene-alt -benzothiadiazole) (F8BT) and 1- (3-methoxycarbonyl) -propyl-1-phenyl- (6,6) C 61 (PCBM) and the like.
상술한 바와 같이 본 발명의 박막형 다공성 유기열전소자는 기존의 상업화 되어 있는 무기열전소자에 비하여 원자재 값이 저렴하여 경제적이며, 열전모듈(module) 제작 공정이 간단하고 대면적화가 용이하면서도 열전효율을 향상시킬 수 있다. 뿐만 아니라 유기태양전지와 본 발명의 유기열전소자를 복합화하여 효율을 극대화할 수 있다.As described above, the thin-film porous organic thermoelectric device of the present invention is economical because the raw material is cheaper than the conventional commercialized inorganic thermoelectric device, and the thermoelectric module manufacturing process is simple and the large area is easy and the thermoelectric efficiency is improved. You can. In addition, the organic solar cell and the organic thermoelectric device of the present invention may be complexed to maximize efficiency.
이하, 실시예는 오로지 본 발명을 보다 구체적으로 설명하기 위한 것으로서, 본 발명의 요지에 따라 본 발명의 범위가 이들 실시예에 의해 제한되지 않는다는 것은 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자에게 있어서 자명할 것이다.Hereinafter, the examples are only for illustrating the present invention in more detail, and the scope of the present invention is not limited by these examples in accordance with the gist of the present invention, those skilled in the art. Will be self-evident.
실시예 1Example 1
유기 열전소자(Organic thermoelectric device) 는 다음과 같은 방법으로 제작되었다. 먼저 Indium Tin Oxide(ITO)가 코팅된 유리기판 위에 정공 운반층인 poly(3-hexylthiophene) (P3HT) 과 발포제(foaming agent) 또는 포로젠(pore gen) 의 유기활성층을 약 10㎚ ~ 100㎛ 두께로 코팅하고 50℃에서 약 15분간 용매를 증발시킨다. 그리고 140℃에서 발포제를 발포시킨다. Organic thermoelectric device was manufactured by the following method. First, on the glass substrate coated with Indium Tin Oxide (ITO), the organic active layer of poly (3-hexylthiophene) (P3HT), a hole transporting layer, and a foaming agent or porogen, is about 10 nm to 100 ㎛ thick. And evaporate the solvent at 50 ° C. for about 15 minutes. And foaming agent is foamed at 140 degreeC.
실시예 2Example 2
유기 열전소자(Organic thermoelectric device) 는 다음과 같은 방법으로 제작되었다. 먼저 Indium Tin Oxide(ITO)가 코팅된 유리기판 위에 정공 운반층인 poly(3-hexylthiophene) (P3HT) 과 전자 운반층인 1-(3-methoxycarbonyl)-propyl-1-phenyl-(6,6)C61 (PCBM), 그리고 발포제(foaming agent) 또는 포로젠(pore gen)을 혼합한 유기활성층을 약 10㎚ ~ 100㎛의 두께로 코팅하고 50℃에서 약 15분간 용매를 증발시킨다. 그리고 140℃에서 발포제를 발포시킨다. 10㎚ ~ 100㎛ 의 유기활성층 내에 나노 또는 마이크로 크기의 다공이 만들어진다. Organic thermoelectric device was manufactured by the following method. First, poly (3-hexylthiophene) (P3HT), a hole transporting layer, and 1- (3-methoxycarbonyl) -propyl-1-phenyl- (6,6), an electron transporting layer, on a glass substrate coated with Indium Tin Oxide (ITO) C61 (PCBM) and an organic active layer mixed with a foaming agent or porogen were coated to a thickness of about 10 nm to 100 μm and the solvent was evaporated at 50 ° C. for about 15 minutes. And foaming agent is foamed at 140 degreeC. Nano or micro sized pores are made in the organic active layer of 10 nm to 100 μm.
실시예 3Example 3
유기 열전소자(Organic thermoelectric device) 는 다음과 같은 방법으로 제작되었다. 먼저 Indium Tin Oxide(ITO)가 코팅된 유리기판 위에 정공 운반층인 poly(3-hexylthiophene) (P3HT) 과 전자 운반층인 poly(9,9-dioctylfluorene-alt-benzothiadiazole) (F8BT), 그리고 발포제(foaming agent) 또는 포로젠(pore gen)를 혼합한 유기활성층을 약 10㎚ ~ 100㎛의 두께로 코팅하고 50℃에서 약 15분간 용매를 증발시킨다. 그리고 140℃에서 발포제를 발포시킨다. 10㎚ ~ 100㎛ 의 유기활성층 내에 나노 또는 마이크로 크기의 다공이 만들어진다. Organic thermoelectric device was manufactured by the following method. First, the hole transport layer poly (3-hexylthiophene) (P3HT), the electron transport layer poly (9,9-dioctylfluorene-alt-benzothiadiazole) (F8BT), and a foaming agent (IT8) were coated on a glass substrate coated with Indium Tin Oxide (ITO). The organic active layer mixed with a foaming agent or porogen (pore gen) is coated to a thickness of about 10nm ~ 100㎛ and the solvent is evaporated at 50 ℃ for about 15 minutes. And foaming agent is foamed at 140 degreeC. Nano or micro sized pores are made in the organic active layer of 10 nm to 100 μm.
실시예 4Example 4
유기 열전소자(Organic thermoelectric device) 는 다음과 같은 방법으로 제작되었다. 먼저 Indium Tin Oxide(ITO)가 코팅된 유리기판 위에 정공 운반층인 poly(3-hexylthiophene) (P3HT) 과 전자 운반층인 TiO2 나노입자(TiO2 Nanoparticles), 그리고 발포제(foaming agent) 또는 포로젠(pore gen) 을 혼합한 유기활성층을 약 10㎚ ~ 100㎛의 두께로 코팅하고 50℃에서 약 15분간 용매를 증발시킨다. 그리고 140℃에서 발포제를 발포시킨다. 10㎚ ~ 100㎛ 의 유기활성층 내에 나노 또는 마이크로 크기의 다공이 만들어진다. Organic thermoelectric device was manufactured by the following method. First, poly (3-hexylthiophene) (P3HT), a hole transporting layer, TiO2 nanoparticles, an electron transporting layer, and a foaming agent or porogen on a glass substrate coated with Indium Tin Oxide (ITO). gen) is mixed with a thickness of about 10 nm to 100 μm and the solvent is evaporated at 50 ° C. for about 15 minutes. And foaming agent is foamed at 140 degreeC. Nano or micro sized pores are made in the organic active layer of 10 nm to 100 μm.
실시예 5Example 5
유기 열전소자(Organic thermoelectric device) 는 다음과 같은 방법으로 제작되었다. 먼저 Indium Tin Oxide(ITO)가 코팅된 유리기판 위에 정공 운반층인 poly(3-hexylthiophene) (P3HT) 과 전자 운반층인 ZnO 나노입자(ZnO Nanoparticles), 그리고 발포제(foaming agent) 또는 포로젠(pore gen) 을 혼합한 유기활성층을 약 10㎚ ~ 100㎛의 두께로 코팅하고 50℃에서 약 15분간 용매를 증발시킨다. 그리고 140℃에서 발포제를 발포시킨다. 10㎚ ~ 100㎛ 의 유기활성층 내에 나노 크기의 다공이 만들어진다.Organic thermoelectric device was manufactured by the following method. First, poly (3-hexylthiophene) (P3HT), a hole transporting layer, ZnO nanoparticles, an electron transporting layer, and a foaming agent or porogen on a glass substrate coated with Indium Tin Oxide (ITO). gen) is mixed with a thickness of about 10 nm to 100 μm and the solvent is evaporated at 50 ° C. for about 15 minutes. And foaming agent is foamed at 140 degreeC. Nano sized pores are made in the organic active layer of 10 nm to 100 μm.
도 1은 본 발명의 유기열전소자 모식도를 나타낸 것이다. 1 shows a schematic diagram of an organic thermoelectric device of the present invention.
(단, 1: 기판, 2: 하부전극, 3: 유기박막층, 4: 구멍, 5: 상부전극)(1, substrate, 2: lower electrode, 3: organic thin film layer, 4: hole, 5: upper electrode)
도 2는 Indium Tin Oxide(ITO)가 코팅된 유리기판 위에 정공 운반층인 poly(3-hexylthiophene) (P3HT) 과 발포제(foaming agent)를 혼합한 혼합용액을 약 10㎚ ~ 100㎛ 두께로 코팅하여 유기활성층을 만들고, 50℃에서 약 15분간 용매를 증발시킨 다음 140℃에서 10분 ~ 2시간 정도 발포제를 발포시켜 SEM(scanning electron microscope)로 이미지를 촬영한 것이다. 이미지에서 볼 수 있듯이 마이크로 크기의 다공들이 많이 생긴 것을 확인할 수 있다. FIG. 2 is coated with a mixed solution of poly (3-hexylthiophene) (P3HT), which is a hole transport layer, and a foaming agent, on a glass substrate coated with Indium Tin Oxide (ITO) to a thickness of about 10 nm to 100 μm. The organic active layer was made, and the solvent was evaporated at 50 ° C. for about 15 minutes, and then foamed with a blowing agent at 140 ° C. for 10 minutes to 2 hours, and the image was taken with a scanning electron microscope (SEM). As you can see in the image, you can see that there are many micro-sized pores.
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| JP2014146680A (en) * | 2013-01-29 | 2014-08-14 | Fujifilm Corp | Thermoelectric conversion material, thermoelectric conversion device and article for thermoelectric power generation and power source for sensor using the same |
| CN105329862A (en) * | 2015-12-04 | 2016-02-17 | 中国科学院福建物质结构研究所 | Method for preparing CsBi<4>Te<6 >thermoelectric material |
| CN109643750A (en) * | 2016-08-10 | 2019-04-16 | 特莫因德股份公司 | Active material and power generator comprising active material |
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| KR20050066337A (en) * | 2003-12-26 | 2005-06-30 | 엘지전자 주식회사 | Manufacturing method of thermoelectric module |
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| JP2014146680A (en) * | 2013-01-29 | 2014-08-14 | Fujifilm Corp | Thermoelectric conversion material, thermoelectric conversion device and article for thermoelectric power generation and power source for sensor using the same |
| CN105329862A (en) * | 2015-12-04 | 2016-02-17 | 中国科学院福建物质结构研究所 | Method for preparing CsBi<4>Te<6 >thermoelectric material |
| CN105329862B (en) * | 2015-12-04 | 2017-10-24 | 中国科学院福建物质结构研究所 | One kind prepares CsBi4Te6The method of thermoelectric material |
| CN109643750A (en) * | 2016-08-10 | 2019-04-16 | 特莫因德股份公司 | Active material and power generator comprising active material |
| KR20190039992A (en) * | 2016-08-10 | 2019-04-16 | 테르모-아이엔디 에스.에이. | Active material and power generator including the same |
| CN109643750B (en) * | 2016-08-10 | 2023-10-31 | 特莫因德股份公司 | Active material and power generator comprising the same |
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