CN112768597B - Method for enhancing thermoelectric performance of organic semiconductor and organic semiconductor thermoelectric device - Google Patents
Method for enhancing thermoelectric performance of organic semiconductor and organic semiconductor thermoelectric device Download PDFInfo
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- CN112768597B CN112768597B CN202110198823.XA CN202110198823A CN112768597B CN 112768597 B CN112768597 B CN 112768597B CN 202110198823 A CN202110198823 A CN 202110198823A CN 112768597 B CN112768597 B CN 112768597B
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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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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/856—Thermoelectric active materials comprising organic compositions
Abstract
The invention provides a method for enhancing the thermoelectric performance of an organic semiconductor and a preparation method of an organic semiconductor thermoelectric device. The method has the advantages of simple process, low cost, universality, high conductivity and larger power factor, thereby being applicable to the field of thermoelectric devices.
Description
Technical Field
The invention belongs to the field of organic semiconductor devices, and particularly relates to a method for enhancing the thermoelectric performance of an organic semiconductor and the organic semiconductor thermoelectric device.
Background
Due to global warming and the shortage of fossil fuels, people tend to find a renewable clean energy source. Thermal energy is a rich energy source, and huge energy exists in our lives in the forms of waste heat, solar heat and body heat. The thermoelectric material can directly convert the renewable heat energy into electric energy through a Seebeck effect (Seebeck effect), namely, two ends of one material are respectively positioned in two environments with different temperatures, the different temperatures of the two ends of a sample can cause uneven distribution of internal carriers, the carrier concentration of the hot end is higher, the carrier concentration of the cold end is lower, and the carriers of the hot end can diffuse to the cold end to form current.
Organic semiconductors have been widely studied and applied to organic thermoelectric devices in recent years due to their advantages of solution processability, flexibility and lightness, low thermal conductivity, high seebeck coefficient, and the like. However, the carrier mobility and conductivity of organic semiconductors are relatively low compared to inorganic semiconductors, which greatly limits the performance of organic semiconductor thermoelectric devices.
In the prior art, the thermoelectric performance of an organic semiconductor is enhanced by adopting a doping mode, but the doping process of the organic semiconductor is not mature, and a universal doping mode cannot be found, so that the development of an organic semiconductor thermoelectric device is limited.
Disclosure of Invention
In order to avoid the defects of the prior art, the invention provides a universal method for enhancing the thermoelectric performance of an organic semiconductor and an organic semiconductor thermoelectric device.
The quantum dot has the advantages of narrow fluorescence half-peak width, excellent absorption performance, relatively high stability, solution processing and the like, is an excellent photoelectric material in recent years, has little application in the thermoelectric field, and utilizes the organic semiconductor/quantum dot heterojunction to enhance the conductivity and power factor of the organic semiconductor material, thereby further improving the thermoelectric performance of the organic semiconductor.
The invention solves the technical problem and adopts the following technical scheme:
a method of enhancing thermoelectric performance of an organic semiconductor, comprising: the organic semiconductor material is used as a main body, the quantum dots are deposited on the organic semiconductor layer to form an organic semiconductor/quantum dot heterojunction, under the illumination condition, a large number of electron hole pairs can be generated in the quantum dots, the electron hole pairs are transmitted to the heterojunction interface, the electron holes are separated, electrons or holes enter the organic semiconductor, the carrier concentration of the organic semiconductor is increased, and therefore the thermoelectric property of the organic semiconductor is improved.
Further, the organic semiconductor material is an N-type or P-type organic semiconductor.
Further, the quantum dots are perovskite quantum dots.
Further, the quantum dots are deposited on the organic semiconductor layer by a solution method or a gas phase method.
Further, the highest occupied molecular orbital HOMO level of the P-type organic semiconductor material is higher than the highest occupied molecular orbital HOMO level of the perovskite quantum dot, or the lowest unoccupied molecular orbital LUMO level of the N-type organic semiconductor material is lower than the lowest unoccupied molecular orbital LUMO level of the perovskite quantum dot.
An organic semiconductor thermoelectric device, characterized in that: the thermoelectric performance of the organic semiconductor is enhanced by adopting the method, and when a temperature difference is formed on the left side and the right side, the cold and hot electrodes can generate current signals.
Further, the substrate is a glass substrate;
further, the cold and hot electrodes are chromium/gold electrodes;
further, the organic semiconductor material is an N-type or P-type organic semiconductor.
Further, the quantum dots are perovskite quantum dots.
Further, the quantum dots are deposited on the organic semiconductor layer by a solution method or a gas phase method.
Further, the highest occupied molecular orbital HOMO level of the P-type organic semiconductor material is higher than the highest occupied molecular orbital HOMO level of the perovskite quantum dot, or the lowest unoccupied molecular orbital LUMO level of the N-type organic semiconductor material is lower than the lowest unoccupied molecular orbital LUMO level of the perovskite quantum dot.
In summary, compared with the prior art, the above technical solutions provided by the present invention can obtain the following beneficial effects:
1) the method provided by the invention is applicable to all organic semiconductors, and the thermoelectric performance can be improved by adopting the method as long as the quantum dots with matched energy levels are found, so that the method is a universal method.
2) The organic semiconductor/quantum dot heterojunction provided by the invention can be used for solution processing, and the quantum dot is directly deposited on the organic semiconductor layer by a solution method, so that the organic semiconductor/quantum dot heterojunction can be formed. The preparation method is simple and feasible, and is suitable for large-scale industrial application.
3) The organic semiconductor/quantum dot heterojunction provided by the invention can greatly improve the conductivity and power factor of the organic semiconductor. The organic semiconductor/quantum dot heterojunction is further applied to the organic thermoelectric device, so that the device performance can be obviously improved.
Drawings
FIG. 1 is a schematic structural diagram of a thermoelectric device to which the PDVT-10/CsPbBr3 QDs heterojunction is applied in the embodiment of the present invention;
FIG. 2 shows the variation of the film conductivity with the illumination intensity after the PDVT-10 and CsPbBr3 QDs form a heterojunction in the embodiment of the invention;
FIG. 3 shows PDVT-10 and CsPbBr in accordance with one embodiment of the present invention3After the QDs form a heterojunction, the power factor of the thermoelectric device is in a change relation with the illumination intensity;
Detailed Description
In order to more clearly illustrate the objects and advantages of the present invention, the following embodiments are further described in detail with reference to the accompanying drawings. The following specific examples are given by way of illustration only and are not intended to be limiting.
The invention adopts perovskite quantum dots such as CsPbBr3QDs and organic semiconductor materials such as PDVT-10 are deposited on the substrate with electrodes by means of solution spin coating, thereby forming PDVT-10/CsPbBr3QDs heterojunctions. Under the irradiation of blue light at 450nm, the film Conductivity (Conductivity) of the PDVT-10 is gradually increased along with the increase of the illumination intensity-4S m-1Lifting to 2.65X 10-1S m-1And the Power Factor (Power Factor) in thermoelectric devices is gradually increased to 1.21 × 10-1μWm-1K-2。
Example 1
Preparation of organic thermoelectric devices
The organic thermoelectric device has a structure of glass substrate/electrode (Cr/Au)/PDVT-10/CsPbBr3QDs. The specific preparation method of example 1 is as follows:
(1) patterned electrodes were prepared on a glass substrate by photolithography and thermal evaporation, the electrodes being Cr/Au (7nm/23 nm).
(2) The glass substrate with the electrode is sequentially subjected to ultrasonic cleaning by deionized water, acetone and isopropanol, then is subjected to ozone treatment and then is transferred into a glove box.
(3) PDVT-10 was dissolved in spectrally pure chlorobenzene in an argon-filled glove box to make a solution with a concentration of 5 mg/mL. The prepared PDVT-10 solution is taken to be coated on the cleaned glass substrate with the electrode in a rotating speed of 1500 rpm, and is annealed for 5 minutes at 180 ℃, thereby preparing the PDVT-10 film.
(4) In an argon-filled glove box, CsPbBr was added3QDs were dissolved in n-hexane to prepare a solution with a concentration of 20 mg/mL. Taking the prepared CsPbBr3The QDs solution was spin-coated on the above-prepared PDVT-10 film at 2000 rpm and annealed at 100 ℃ for 10 minutes, thereby fabricating the thermoelectric device shown in FIG. 1.
(5) The thermoelectric device was heated on the thermoelectric side and the current-voltage relationship of the device was tested using a Keithley 2912A semiconductor analyzer to calculate the conductivity and power factor of the film. The conductivity and power factor of the film as a function of the illumination intensity are shown in FIGS. 2 and 3.
Claims (6)
1. A method of enhancing thermoelectric performance of an organic semiconductor, comprising: the organic semiconductor material is used as a main body, the quantum dots are deposited on the organic semiconductor layer to form an organic semiconductor/quantum dot heterojunction, under the illumination condition, a large number of electron hole pairs can be generated in the quantum dots, the electron hole pairs are transmitted to the heterojunction interface, the electron holes are separated, electrons or holes enter the organic semiconductor, the carrier concentration of the organic semiconductor is increased, and the thermoelectric property of the organic semiconductor is improved; the organic semiconductor material is an N-type or P-type organic semiconductor material; the highest occupied molecular orbital HOMO energy level of the P-type organic semiconductor material is higher than the highest occupied molecular orbital HOMO energy level of the perovskite quantum dot, or the lowest unoccupied molecular orbital LUMO energy level of the N-type organic semiconductor material is lower than the lowest unoccupied molecular orbital LUMO energy level of the perovskite quantum dot.
2. A method for enhancing thermoelectric performance of an organic semiconductor as recited in claim 1, wherein said quantum dots are perovskite quantum dots.
3. A method for enhancing thermoelectric performance of an organic semiconductor as recited in claim 1, wherein the quantum dots are deposited on the organic semiconductor layer using a solution process or a vapor phase process.
4. An organic semiconductor thermoelectric device, characterized in that: a thermoelectric performance of the organic semiconductor is enhanced by the method as claimed in any one of claims 1 to 3 by forming a thermoelectric electrode above a substrate and depositing an organic semiconductor layer above the thermoelectric electrode, and a current signal is generated between the thermoelectric electrode and the thermoelectric electrode when a temperature difference is formed between the left and right sides.
5. An organic semiconducting thermoelectric device according to claim 4, wherein the quantum dots are perovskite quantum dots.
6. An organic semiconducting thermoelectric device as claimed in claim 4 wherein the quantum dots are deposited onto the organic semiconducting layer using a solution or gas phase process.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103500792A (en) * | 2013-09-18 | 2014-01-08 | 同济大学 | Method for preparing carbon nano tube/poly (3-hexyl) thiophene composite thermoelectric materials |
| CN108365104A (en) * | 2018-03-29 | 2018-08-03 | 南开大学 | A kind of hybrid n-type semiconductor thin-film material based on nanocrystal |
| CN108428799A (en) * | 2018-04-13 | 2018-08-21 | 南开大学 | A kind of hybrid p-type semiconductor thin-film material based on nanocrystal |
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| US20130276851A1 (en) * | 2012-04-20 | 2013-10-24 | Acreo Swedish Ict Ab | Thermoelectric device |
| JP2018022828A (en) * | 2016-08-05 | 2018-02-08 | シャープ株式会社 | Thermoelectric conversion element |
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| CN103500792A (en) * | 2013-09-18 | 2014-01-08 | 同济大学 | Method for preparing carbon nano tube/poly (3-hexyl) thiophene composite thermoelectric materials |
| CN108365104A (en) * | 2018-03-29 | 2018-08-03 | 南开大学 | A kind of hybrid n-type semiconductor thin-film material based on nanocrystal |
| CN108428799A (en) * | 2018-04-13 | 2018-08-21 | 南开大学 | A kind of hybrid p-type semiconductor thin-film material based on nanocrystal |
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