CN110581220A - semitransparent organic solar cell device with heat insulation and temperature control effects and preparation method thereof - Google Patents

semitransparent organic solar cell device with heat insulation and temperature control effects and preparation method thereof Download PDF

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CN110581220A
CN110581220A CN201910815871.1A CN201910815871A CN110581220A CN 110581220 A CN110581220 A CN 110581220A CN 201910815871 A CN201910815871 A CN 201910815871A CN 110581220 A CN110581220 A CN 110581220A
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solar cell
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李昌治
李雪
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Zhejiang University ZJU
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
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    • Y02E10/549—Organic PV cells

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Abstract

The invention discloses a semitransparent organic solar cell device with heat insulation and temperature control effects, which structurally comprises a substrate, a cathode modification layer, an organic active layer, an anode modification layer, an anode and a photonic crystal (Bragg dielectric mirror). Wherein the organic active layer is a blended film of a polymer electron donor PTB7-Th and a small molecule electron acceptor IFIC-i-4F. By utilizing the strong absorption of PTB7-Th and IFIC-i-4F in the near infrared band and by means of the regulation and control of the photonic crystal on the light absorption range and the intensity, the device realizes the high transmission of 380-780nm visible light band and the high blocking capability of 780-2500nm near infrared band. Compared with a binary simple organic semi-transparent solar cell based on PTB7-Th IFIC-i-4F, after photonic crystals are introduced, the average visible light transmittance (AVT) is improved from 24.5% to 29.5%, the improvement amplitude is up to 20%, the infrared blocking rate (IRR) is improved from 90.0% to 93.1%, the energy conversion efficiency (PCE) is almost unchanged and is kept above 7%, and the method is one of the highest records of the comprehensive performance of the current multifunctional semi-transparent organic solar cell.

Description

Semitransparent organic solar cell device with heat insulation and temperature control effects and preparation method thereof
Technical Field
The invention relates to a semitransparent organic solar cell, in particular to a multifunctional semitransparent organic solar cell with heat insulation and temperature control effects.
Background
In addition to clean energy power generation, energy conservation also plays an important role in maintaining sustainability of the human society. Since the energy source for building cooling accounts for a large part of the global energy consumption each year, it has prompted us to explore translucent organic solar cells with organic layer functionalities of hundred nanometers thickness such as visual perspective, photoelectric conversion, and near infrared/infrared photon suppression, which are very important for future power window and building integration.
The traditional organic solar cell is an opaque solar cell device with an electrode of 100nm thickness, an active layer material with strong near infrared absorption and weak visible light absorption is screened out, the thickness of the electrode can be optimized to enhance the transmittance, and the simple semitransparent organic solar cell is obtained. But the performance indexes are all low, which is not favorable for future large-scale commercial application.
In the prior art, various performances of the semitransparent organic solar cell can be improved by introducing the photonic crystal. However, there are still significant challenges to achieving this goal, particularly to achieve a fine balance between key parameters, such as Power Conversion Efficiency (PCE), average visible light transmittance (AVT), and IR Rejection Ratio (IRR) of the device. The complex balancing and uncertain structure-property relationships that exist between materials, devices and interfaces remain significant challenges.
Disclosure of Invention
the invention aims to overcome the defect of simplification of the functions of an organic solar cell, develop a multifunctional high-efficiency semitransparent organic solar cell and provide a preparation method and a process for preparing a high-efficiency semitransparent solar cell device with heat insulation and temperature control.
The technical scheme adopted by the invention is as follows:
A semitransparent organic solar cell device with heat insulation and temperature control effects is of a multilayer laminated structure from bottom to topThe anode modification layer, the organic active layer, the cathode modification layer, the cathode and the photonic crystal layer are sequentially arranged on the substrate; wherein the photonic crystal layer consists of LiF layer and TeO layer2The layers are alternately superposed.
Preferably, a layer of LiF is overlaid with a layer of TeO2One round of alternation is adopted, and LiF and TeO are in the photonic crystal layer2There are at least two rounds alternating.
Further, LiF and TeO in the photonic crystal layer2Preferably two alternating rounds.
As further preferred for the above three implementations, the specific selection of materials for each layer is as follows: the substrate is glass; the anode is ITO; the anode modification layer is PEDOT, PSS; the organic active layer is a blended film formed by an electron donor material PTB7-Th and an electron acceptor material IFIC-i-4F; the cathode modification layer is Bis-FIMG; the cathode is Ag;
The PTB7-Th has a chemical structural formula as follows:
wherein n is more than or equal to 10;
The chemical structural formula of the IFIC-i-4F is as follows:
The chemical structural formula of the Bis-FIMG is as follows:
Further, the thickness of each layer material is optimized as follows: the thickness of the organic active layer is 88nm, the thickness of the cathode modification layer is 12nm, the thickness of the cathode is 16nm, and the photonic crystal layer sequentially comprises a LiF layer with the thickness of 10nm and TeO with the thickness of 20nm from bottom to top2layer, 120nm LiF layer, 100nm TeO2And (3) layer composition.
Another object of the present invention is to provide a method for preparing any one of the above multifunctional semitransparent organic solar cell devices, which comprises the following steps:
Firstly, spin-coating a layer of PEDOT (PSS) on the surface of transparent conductive glass with strip ITO etched on the surface, and then annealing the PEDOT, PSS; then spin-coating the binary organic material mixed solution containing the electron donor material PTB7-Th and the electron acceptor material IFIC-i-4F on PEDOT, PSS, in an anhydrous and oxygen-free environment to obtain an organic active layer; then, a layer of Bis-FIMG solution is spin-coated on the organic active layer; finally, an Ag electrode is evaporated on the Bis-FIMG by using an evaporation instrument, and LiF layers and TeO are alternately and overlappingly evaporated on the Ag electrode2A layer; finally, the multifunctional semitransparent organic solar cell device with the heat insulation and temperature control effects is obtained.
Preferably, in the preparation method, the mass ratio of the electron donor material PTB7-Th to the electron acceptor material IFIC-i-4F is 1:1-1:2, and more preferably 1: 1.8.
Preferably, the Bis-FIMG solution has a Bis-FIMG concentration of 0.5 to 2mg/mL, more preferably 1 mg/mL.
The invention has the advantage that the overall performance of the device is improved by introducing the photonic crystal on the thin-layer silver electrode. On the basis of a semitransparent organic solar cell device obtained by optimizing the thickness of an active layer, the thickness of an electron transmission layer and the thickness of a silver electrode, photonic crystals are introduced to improve the transmittance of the device to a visible light region and the blocking capability of the device to an infrared band. The thickness of silver evaporated on the optimized simple semitransparent device is 16nm, the AVT, IRR and PCE of the optimized simple semitransparent device are respectively 24.5%, 90.0% and 7.6%, and a photonic crystal layer LiF (10nm) and TeO are introduced on the optimized semitransparent device2(20nm),LiF(120nm),TeO2after (100nm), the maximum transmission peak value of the whole device to visible light is shifted to about 500nm, the distribution of the visible light sensitivity curve is closer to that of a human eye, the average transmittance of the device is greatly increased, and in addition, the blocking capability of the device to near infrared light is stronger due to the introduction of the photonic crystal. The AVT of the semitransparent organic solar cell device added with the photonic crystal is improved to 29.5 percent, and compared with the common semitransparent device without the photonic crystalThe lifting amplitude is up to 20%, the IRR is also lifted to 93.1% from the original 90.0%, and most importantly, after the photonic crystal is added, the PCE of the whole device is hardly changed and still remains over 7%.
Drawings
FIG. 1 shows the absorption spectra of PTB7-Th, IFIC-i-4F, Bis-FIMG, PEDOT: PSS.
fig. 2 is a graph of the transmittance and thickness of the devices J-V, EQE for different silver electrode thicknesses in comparative example 1.
fig. 3 is a CIE diagram of the silver electrode devices of different thicknesses in comparative example 1.
Fig. 4 is a graph of J-V, CIE, transmittance, and EQE of the device in example 1, where a represents the device prepared in comparative example 1 (16 nm silver electrode evaporated only), B represents the device prepared in example 1 (16 nm silver electrode evaporated + DBR), where fig. C is the device prepared in comparative example 1, and fig. D is the device prepared in example 1.
Detailed Description
The invention will be further elucidated and described with reference to the drawings and the detailed description.
The multifunctional high-efficiency semitransparent organic solar cell device with the heat insulation and temperature control effects is of a multilayer layered structure, and the structure sequentially comprises a substrate, an anode modification layer, an organic active layer, a cathode modification layer, a cathode and a photonic crystal layer from bottom to top. Wherein the photonic crystal layer (DBR) is composed of LiF layer and TeO layer2The layers are alternately superposed. A layer of TeO is superimposed on a layer of LiF2The photonic crystal layer of the invention comprises LiF and TeO in a round of alternation2There are at least two rounds alternating. LiF and TeO in the photonic crystal layer due to the process complexity increased by too many alternating turns2Preferably, two rounds of alternating are adopted, namely the photonic crystal layer adopts a four-layer structure and sequentially comprises LiF and TeO from bottom to top2、LiF、TeO2。
In a solar cell device, the specific materials of the remaining layers may be selected as desired. In one implementation of the invention, the following may be chosen: the substrate is conductive glass, the anode is ITO, and the anode modification layer is PEDOT PSS. The organic active layer is a blended film of a polymer electron donor PTB7-Th and a small molecule electron acceptor IFIC-i-4, and the specific structural formulas of the three compounds of the cathode modification layer is Bis-FIMG, PTB7-Th, IFIC-i-4 and Bis-FIMG are described in the summary of the invention. By utilizing the characteristics of weak visible light absorption, strong near infrared absorption, high Bis-FIMG conductivity and the like of PTB7-Th and IFIC-i-4F, common semitransparent organic solar cell devices with different performances can be obtained by adjusting the thickness of the silver electrode. After the photonic crystal layer is introduced into the optimized common semitransparent organic solar cell device, the transmission peak value of the device in a visible light area can be shifted to about 500nm, and the device is more matched with a human eye photosensitive curve, so that the AVT is greatly improved.
in the device, various performances of the semitransparent solar cell can be improved by optimizing the thickness of each layer of photonic crystal. The performance of the device as a semitransparent organic solar cell is mainly reflected on energy conversion efficiency (PCE) and average visible light transmittance (AVT), wherein the energy conversion efficiency refers to the energy conversion capability of the organic solar cell, and the average visible light transmittance refers to the transmittance of the organic solar cell relative to the photosensitive response of human eyes in a 380nm-780nm interval. The thickness of the silver electrode has great influence on two indexes, the thickness of the silver electrode is large, the energy conversion efficiency is high, and the average transmittance is low; the silver electrode has small thickness, low energy conversion efficiency and high average transmittance. The optimized thin-layer silver electrode has good transmittance and high conductivity. The two substances in the photonic crystal have weak absorption and large refractive index difference in the whole wave band range, the low refractive index substance and the high refractive index substance are alternately overlapped from bottom to top in sequence, the respective thickness needs to be specifically determined through optical simulation, and the specific reference of the number of the overlapped layers is optical simulation guidance.
The effect of the multifunctional high-efficiency organic semitransparent solar cell device with heat insulation and temperature control effects is proved by comparing a best embodiment with a common semitransparent organic solar cell device. However, it should be noted that the following examples are only the best examples of the device of the present invention as a multifunctional high-efficiency organic semi-transparent solar cell device with thermal insulation and temperature control effects, and are not intended to limit the scope of the present invention. The thickness of the silver electrode, the composition and thickness of the photonic crystal can be adjusted by those skilled in the art according to actual conditions, and further optimized according to needs.
Comparative example 1
sequentially carrying out ultrasonic oscillation cleaning on transparent conductive glass with strip-shaped ITO (cathode) etched on the surface by using alkali liquor, deionized water, acetone, isopropanol and ethanol, drying, and then carrying out ultraviolet ozone treatment for 15 minutes; and then, a layer of PEDOT: PSS is spin-coated on the surface of the conductive glass, the rotating speed is 4000rpm, the spin-coating time is 40 seconds, and then the annealing treatment is carried out for 20 minutes at 140 ℃. The sheets were then transferred to a glove box, and the PTB7-Th: the IFIC-i-4F mixed solution of PTB7-Th and IFIC-i-4F with the mass ratio of 1:1.8 and the total concentration of 20mg/mL is spin-coated for 60 seconds at the rotating speed of 2500rpm to obtain an active layer with the thickness of 88nm, and then 1mg/mL Bis-FIMG solution is spin-coated on the active layer at the rotating speed of 3000rpm to form a cathode modification layer with the thickness of 12 nm. Finally, three Ag electrodes (cathodes) with different thicknesses (12nm,16nm and 20nm) are evaporated by an evaporator, so that three effective areas with different cathode thicknesses of 5.8mm are obtained2A common translucent device. The solar cell device sequentially comprises glass/ITO/PEDOT, PSS/PTB7-Th, IFIC-i-4F/Bis-FIMG/Ag and a film layer, wherein the glass/ITO/PEDOT, the PSS/PTB7-Th and the IFIC-i-4F/Bis-FIMG/Ag are arranged from bottom to top.
the illumination intensity is 100mW/cm2The current-voltage curve of the device is tested under the irradiation of AM1.5G simulated sunlight, wherein the open-circuit voltage of a silver electrode with the thickness of 16nm is 0.66V, and the open-circuit current density is 18.6mA/cm2The filling factor is 0.62, the PCE is 7.6%, the transmission spectrum is obtained by testing with an ultraviolet photometer, and the AVT and the IRR (infrared blocking rate) are respectively 24.5% and 90.0% by calculation.
As shown in fig. 2 (a), (B), (C), PCE (7.6%) and AVT (24.5%) of the semitransparent organic solar cell device reached a balance when the active layer was 88nm thick, the electron transport layer was 12nm thick, and the silver electrode was 16 nm. For silver electrode devices with thicknesses of 12nm,16nm and 20nm, the corresponding transmission chromaticities according to the transmittance spectrum are shown in fig. 3.
Example 1
Sequentially carrying out ultrasonic oscillation cleaning on transparent conductive glass with strip-shaped ITO (cathode) etched on the surface by using alkali liquor, deionized water, acetone, isopropanol and ethanol, drying, and then carrying out ultraviolet ozone treatment for 15 minutes; PSS is coated on the surface of the conductive glass in a spinning mode, the rotating speed is 4000rpm, the spinning time is 40 seconds, and then annealing treatment is carried out for 20 minutes at the temperature of 140 ℃. The sheets were then transferred to a glove box, and the PTB7-Th: the IFIC-i-4F mixed solution of PTB7-Th and IFIC-i-4F with the mass ratio of 1:1.8 and the total concentration of 20mg/mL is spin-coated for 60 seconds at the rotating speed of 2500rpm to obtain an active layer with the thickness of 88nm, and then 1mg/mL Bis-FIMG solution is spin-coated on the active layer at the rotating speed of 3000 rpm. Finally, an Ag electrode (cathode) with the thickness of 16nm is evaporated by an evaporator, and then LiF (thickness of 10nm) and TeO are continuously evaporated on the surface of the Ag electrode in sequence2(thickness 20nm), LiF (thickness 120nm), TeO2(thickness 100nm) to give an effective area of 5.8mm2The multifunctional translucent device of (1). The solar cell device sequentially comprises glass/ITO/PEDOT, PSS/PTB7-Th, IFIC-i-4F/Bis-FIMG/Ag/LiF/TeO from bottom to top2/LiF/TeO2。
The illumination intensity is 100mW/cm2The current-voltage curve of the device is tested under the irradiation of AM1.5G simulated sunlight, and the open-circuit voltage is 0.66V and the open-circuit current density is 17.3mA/cm2The filling factor is 0.64, the PCE is 7.3%, the transmission spectrum is obtained by testing with an ultraviolet photometer, and the AVT and the IRR are respectively 29.5% and 93.1% by calculation.
In comparison with comparative example 1, when the thickness of the active layer was 88nm, the thickness of the electron transport layer was 12nm, and the silver electrode was 16nm, LiF (10nm), TeO, was added to the silver electrode from the bottom up2(20nm),LiF(120nm),TeO2When the photonic crystal is (100nm), the overall performance of the device is improved as a whole, as shown in (C) and (D) in FIG. 4, the AVT is improved from 24.5% to 29.5%, the improvement amplitude is up to 20%, the infrared blocking ratio (IRR) is improved from 90.0% to 93.1%, the color coordinates of the device added with the DBR are closer to the white point coordinates (0.33 ), as shown in (B) in FIG. 4. As shown in FIG. 4 (A), (C), (D), the increase of DBR hardly causes JSCAnd the EQE is reduced, the whole PCE remains almost unchanged, all at above 7%.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A semitransparent organic solar cell device with heat insulation and temperature control effects is characterized in that the device is of a multilayer laminated structure and sequentially comprises a substrate, an anode modification layer, an organic active layer, a cathode modification layer, a cathode and a photonic crystal layer from bottom to top; wherein the photonic crystal layer consists of LiF layer and TeO layer2The layers are alternately superposed.
2. The multifunctional semitransparent organic solar cell device with thermal insulating and temperature controlling effects of claim 1 wherein said multifunctional semitransparent organic solar cell device is formed by stacking a layer of LiF on a layer of TeO2One round of alternation is adopted, and LiF and TeO are in the photonic crystal layer2There are at least two rounds alternating.
3. The translucent organic solar cell device with thermal insulation and control of temperature of claim 2, wherein said photonic crystal layer comprises LiF and TeO2Preferably two alternating rounds.
4. A translucent organic solar cell device with thermal insulation and temperature control effect according to any one of claims 1 to 3, characterised in that the substrate is glass; the anode is ITO; the anode modification layer is PEDOT, PSS; the organic active layer is a blended film formed by an electron donor material PTB7-Th and an electron acceptor material IFIC-i-4F; the cathode modification layer is Bis-FIMG; the cathode is Ag;
The PTB7-Th has a chemical structural formula as follows:
Wherein n is more than or equal to 10;
The chemical structural formula of the IFIC-i-4F is as follows:
The chemical structural formula of the Bis-FIMG is as follows:
5. The translucent organic solar cell device with thermal insulation and temperature control effects of claim 4, wherein the thickness of the organic active layer is 88nm, the thickness of the cathode modification layer is 12nm, the thickness of the cathode is 16nm, and the photonic crystal layer sequentially comprises a LiF layer with the thickness of 10nm and a TeO layer with the thickness of 20nm from bottom to top2Layer, 120nm LiF layer, 100nm TeO2And (3) layer composition.
6. A method for manufacturing a translucent organic solar cell device according to claim 4, characterized in that it comprises the following steps:
firstly, spin-coating a layer of PEDOT (PSS) on the surface of transparent conductive glass with strip ITO etched on the surface, and then annealing the PEDOT, PSS; then spin-coating the binary organic material mixed solution containing the electron donor material PTB7-Th and the electron acceptor material IFIC-i-4F on PEDOT, PSS, in an anhydrous and oxygen-free environment to obtain an organic active layer; then, a layer of Bis-FIMG solution is spin-coated on the organic active layer; finally, an Ag electrode is evaporated on the Bis-FIMG by using an evaporation instrument, and LiF layers and TeO are alternately and overlappingly evaporated on the Ag electrode2A layer; finally, the multifunctional semitransparent organic solar cell device with the heat insulation and temperature control effects is obtained.
7. The process according to claim 6, wherein the mass ratio of the electron donor material PTB7-Th to the electron acceptor material IFIC-i-4F is 1:1 to 1: 2.
8. The process according to claim 7, wherein the mass ratio of the electron donor material PTB7-Th to the electron acceptor material IFIC-i-4F is preferably 1: 1.8.
9. the method of claim 6, wherein the Bis-FIMG solution has a Bis-FIMG concentration of 0.5 to 2 mg/mL.
10. The method of claim 9, wherein the Bis-FIMG solution has a Bis-FIMG concentration of preferably 1 mg/mL.
CN201910815871.1A 2019-08-30 2019-08-30 semitransparent organic solar cell device with heat insulation and temperature control effects and preparation method thereof Pending CN110581220A (en)

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