CN110828685B - Carbon quantum dot @ zinc oxide composite nano material and preparation and application thereof - Google Patents

Carbon quantum dot @ zinc oxide composite nano material and preparation and application thereof Download PDF

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CN110828685B
CN110828685B CN201911160597.5A CN201911160597A CN110828685B CN 110828685 B CN110828685 B CN 110828685B CN 201911160597 A CN201911160597 A CN 201911160597A CN 110828685 B CN110828685 B CN 110828685B
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carbon quantum
zinc oxide
quantum dot
oxide composite
methanol
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CN110828685A (en
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闫翎鹏
赵文盛
杨永珍
谷惠民
王亚玲
马昌期
王�华
刘旭光
许并社
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Taiyuan University of Technology
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Abstract

The invention discloses a carbon quantum dot @ zinc oxide (CQDs @ ZnO) composite nanomaterial, which is obtained by adding a carbon quantum dot and an anhydrous methanol mixed solution of potassium hydroxide into an anhydrous methanol solution of zinc acetate to react by adopting an in-situ synthesis method. The carbon quantum dot @ zinc oxide composite nanomaterial improves the defects on the surface and inside of a pure zinc oxide nanomaterial and improves the stability of the zinc oxide nanomaterial. The organic solar cell cathode interface layer material is applied to an inverted organic solar cell and can improve the photoelectric conversion efficiency of the organic solar cell as the organic solar cell cathode interface layer material.

Description

Carbon quantum dot @ zinc oxide composite nano material and preparation and application thereof
Technical Field
The invention belongs to the technical field of organic solar cells, relates to a cathode interface layer material for an organic solar cell, and particularly relates to a carbon quantum dot @ zinc oxide (CQDs @ ZnO) composite nano material capable of being used as a cathode interface layer material, and a preparation method of the composite nano material.
Background
Since the new century, the energy crisis and environmental problems are increasingly prominent, and people seek cleaner renewable energy. The solar cell can convert light energy into electric energy, and the light energy is inexhaustible.
In recent years, organic solar cells have attracted attention of researchers due to their advantages such as being light and flexible, being capable of printing on a large area, and being integrated into photovoltaic cells. However, the current organic solar cell has low photoelectric conversion efficiency, which becomes a bottleneck restricting the development of the organic solar cell.
The organic solar cell mainly comprises a glass substrate, a cathode interface layer, an organic active layer, an anode interface layer and an anode 6-layer material. Researchers modify the 6 layers of materials from different directions in order to improve the efficiency of the organic solar cell, and one of the modifications is to modify the cathode interface layer material.
Zinc oxide nanoparticles are widely used as cathode interface layer (ETL) material of organic solar cells due to their excellent properties. However, pure zinc oxide nanoparticles have a large number of surface and internal defects, and the defects inhibit the charge transfer efficiency, thereby affecting the photoelectric conversion efficiency of the organic solar cell and limiting the further application of the organic solar cell.
The modification treatment aiming at the zinc oxide nano-particles at present comprises small molecule modification of the zinc oxide and preparation of a compound by doping the zinc oxide. T, Stubhan and the like (Inverted organic solar cells using a luminescence processed aluminum-doped zinc oxide layer, 12 (2011): 1539-. Although the mode of modifying zinc oxide can improve the electron mobility of zinc oxide, the effect of improving the surface defects of the zinc oxide is limited, the preparation process is complex, the zinc oxide needs to be treated at high temperature of 260 ℃, and the requirement of mass production cannot be met.
J.F. Wei et al (Silane-capped ZnO nanoparticles for use as the electron transport layer in inverted organic solar cells. ACS Nano, 2018, 12: 5518-5529.) utilize Silane to coat nano zinc oxide, improve the dispersion stability of zinc oxide and inhibit the surface defects thereof, but the introduction of functional groups reduces the electron mobility of zinc oxide, which is not beneficial to improving the photoelectric conversion efficiency of organic solar cells.
Disclosure of Invention
The invention aims to provide a carbon quantum dot @ zinc oxide (CQDs @ ZnO) composite nano material and a preparation method of the composite nano material. The composite nano material provided by the invention is used as a cathode interface layer material of an organic solar cell, so that the photoelectric conversion efficiency of the organic solar cell and the stability of the zinc oxide nano material can be improved.
The carbon quantum dot @ zinc oxide composite nanomaterial is obtained by adding a carbon quantum dot and an anhydrous methanol mixed solution of potassium hydroxide into an anhydrous methanol solution of zinc acetate to react by adopting an in-situ synthesis method.
Specifically, in the carbon quantum dot @ zinc oxide composite nanomaterial, the mass ratio of the carbon quantum dot to the zinc oxide is 0.1-20: 100.
More specifically, the mass ratio of the carbon quantum dots to the zinc oxide is preferably 0.5-5: 100.
The carbon quantum dot @ zinc oxide composite nano material is prepared by the following method: dispersing carbon quantum dots in absolute methanol, adding a potassium hydroxide absolute methanol solution to obtain a methanol mixed solution of potassium hydroxide and the carbon quantum dots, dropwise adding a zinc acetate absolute methanol solution heated to 62-64 ℃ to react, standing to precipitate, washing and drying to obtain the carbon quantum dot @ zinc oxide composite nano material.
In the preparation method of the carbon quantum dot @ zinc oxide composite nanomaterial, the reaction is carried out by stirring at the temperature of 62-64 ℃, and the reaction time is not less than 1.5 h.
In the reaction process, after the methanol mixed solution is dripped, white precipitate is generated firstly, the solution becomes clear after the stirring reaction is carried out for a period of time, and the precipitate is generated again after the stirring reaction is carried out for a period of time.
After the reaction is finished, the reaction product is cooled to room temperature and stands for not less than 4 hours, so that the precipitate is separated out and completely settled.
Preferably, the method adopts an ultrasonic treatment mode, the carbon quantum dots are respectively dispersed in the anhydrous methanol in an ultrasonic mode, the potassium hydroxide is dissolved in the anhydrous methanol in an ultrasonic mode, the carbon quantum dot methanol dispersion liquid is mixed with the potassium hydroxide methanol solution, and the methanol mixed liquid of the potassium hydroxide and the carbon quantum dots is obtained through ultrasonic dispersion.
The carbon quantum dot @ zinc oxide composite nanomaterial prepared by the method can be used as a cathode interface layer material and applied to the preparation of organic solar cells.
The carbon quantum dot @ zinc oxide composite nanomaterial is prepared by an in-situ synthesis method, the defects on the surface and inside of a pure zinc oxide nanomaterial are overcome, and the carbon quantum dot @ zinc oxide composite nanomaterial can effectively improve the photoelectric conversion efficiency and stability of an organic solar cell by applying the carbon quantum dot @ zinc oxide composite nanomaterial to an inverted organic solar cell.
The carbon quantum dot @ zinc oxide composite nanomaterial is used for preparing a cathode interface layer of an organic solar cell, and the cathode interface layer is matched with different organic active layers to prepare the organic solar cell.
The preparation method of the carbon quantum dot @ zinc oxide composite nanomaterial is simple and efficient, and the used raw materials are non-toxic and harmless to the environment and are suitable for large-scale industrial application.
Drawings
FIG. 1 is a TEM image of the preparation of a zinc oxide nanomaterial (a) in comparative example 1 and the preparation of carbon quantum dot @ zinc oxide composite nanomaterials (b-d) in examples 1, 2 and 3.
Fig. 2 is a graph of the uv-vis absorption spectra of the zinc oxide nanomaterial prepared in comparative example 1 and the carbon quantum dot @ zinc oxide composite nanomaterials prepared in examples 1, 2 and 3.
Fig. 3 is a photoluminescence spectrum of the zinc oxide nanomaterial prepared in comparative example 1 and the carbon quantum dot @ zinc oxide composite nanomaterials prepared in examples 1, 2 and 3.
Fig. 4 is an X-ray diffraction pattern of the zinc oxide nanomaterial prepared in comparative example 1 and the carbon quantum dot @ zinc oxide composite nanomaterials prepared in examples 1 and 3.
Fig. 5 is a graph showing current density and voltage characteristics of organic solar cells prepared in examples 6, 7, 8 and comparative example 2.
Fig. 6 is a graph of external quantum efficiency of organic solar cells prepared in examples 6, 7, 8 and comparative example 2.
Fig. 7 is a graph showing current density and voltage characteristics of organic solar cells prepared in examples 9, 10, 11 and comparative example 3.
Fig. 8 is a graph of external quantum efficiency of organic solar cells prepared in examples 9, 10, 11 and comparative example 3.
Detailed Description
The following examples further describe embodiments of the present invention. The following examples are only for illustrating the technical solutions of the present invention more clearly, and do not limit the scope of the present invention. Various changes, modifications, substitutions and alterations to these embodiments will be apparent to those skilled in the art without departing from the principles and spirit of this invention.
Example 1.
0.0055g of carbon quantum dots was weighed, added to 10mL of anhydrous methanol, and ultrasonically dispersed for 5 min.
0.74g of potassium hydroxide was weighed, added to 23mL of anhydrous methanol, and dissolved for 5min with ultrasound.
And mixing the prepared carbon quantum dot methanol dispersion liquid with a potassium hydroxide methanol solution, and performing ultrasonic dispersion.
Weighing 1.475g of zinc acetate, adding the zinc acetate into 63mL of anhydrous methanol, heating to 62 ℃ under stirring, keeping the temperature, and dropwise adding the mixed solution of the potassium hydroxide and the methanol with the carbon quantum dots at a constant speed within 10 min.
After the methanol mixed solution is dripped, the temperature is kept and the stirring is continued, white precipitate is generated after 10min, the solution becomes clear after 15min, and precipitate is generated again after 1.2 h. After 1.5h, the heating and stirring were stopped, and after standing for 4h, the product settled completely.
And (3) discarding the supernatant, washing the product with anhydrous methanol for 2 times, and centrifuging to obtain the CQDs @ ZnO composite nano material with the carbon quantum dot content of 1%.
Example 2.
0.011g of carbon quantum dots are weighed and added into 10mL of anhydrous methanol, and ultrasonic dispersion is carried out for 5 min.
0.74g of potassium hydroxide was weighed, added to 23mL of anhydrous methanol, and dissolved for 5min with ultrasound.
And mixing the prepared carbon quantum dot methanol dispersion liquid with a potassium hydroxide methanol solution, and performing ultrasonic dispersion.
Weighing 1.475g of zinc acetate, adding the zinc acetate into 63mL of anhydrous methanol, heating to 63 ℃ under stirring, keeping the temperature, and dropwise adding the mixed solution of the potassium hydroxide and the methanol with the carbon quantum dots at a constant speed within 9 min.
After the methanol mixed solution is dripped, the temperature is kept and the stirring is continued, white precipitate is generated after 9min, the solution becomes clear after 13min, and precipitate is generated again after 1.1 h. After 1.5h, the heating and stirring were stopped, and after standing for 4h, the product settled completely.
And (3) discarding the supernatant, washing the product with anhydrous methanol for 2 times, and centrifuging to obtain the CQDs @ ZnO composite nano material with the carbon quantum dot content of 2%.
Example 3.
0.0165g of carbon quantum dots are weighed, added into 15mL of anhydrous methanol, and ultrasonically dispersed for 5 min.
0.74g of potassium hydroxide was weighed, added to 18mL of anhydrous methanol, and dissolved for 5min with ultrasound.
And mixing the prepared carbon quantum dot methanol dispersion liquid with a potassium hydroxide methanol solution, and performing ultrasonic dispersion.
Weighing 1.475g of zinc acetate, adding the zinc acetate into 63mL of anhydrous methanol, heating to 64 ℃ under stirring, keeping the temperature, and dropwise adding the mixed solution of the potassium hydroxide and the methanol with the carbon quantum dots at a constant speed within 8 min.
After the methanol mixed solution is dripped, the temperature is kept and the stirring is continued, white precipitate is generated after 9min, the solution becomes clear after 11min, and precipitate is generated again after 1 h. After 1.5h, the heating and stirring were stopped, and after standing for 4h, the product settled completely.
And (3) discarding the supernatant, washing the product with anhydrous methanol for 2 times, and centrifuging to obtain the CQDs @ ZnO composite nano material with the carbon quantum dot content of 3%.
Comparative example 1.
0.74g of potassium hydroxide is weighed, added into 23mL of anhydrous methanol, and dissolved for 5min by ultrasonic wave to obtain a potassium hydroxide methanol solution.
Weighing 1.475g of zinc acetate, adding the zinc acetate into 63mL of anhydrous methanol, heating to 62 ℃ under stirring, keeping the temperature, and dropwise adding the potassium hydroxide methanol solution at a constant speed within 10 min.
After the dropwise addition, the temperature is kept and stirring is continued, white precipitate is generated after 12min, the solution becomes clear after 17min, and precipitate is generated again after 1.2 h. After 1.5h, the heating and stirring were stopped, and after standing for 4h, the product settled completely.
And (4) discarding the supernatant, washing the product with anhydrous methanol for 2 times, and centrifuging to obtain the pure zinc oxide nano material.
FIG. 1 shows TEM images of zinc oxide nano-materials (a) prepared in comparative example 1 and CQDs @ ZnO composite nano-materials (b-d) prepared in examples 1-3. As can be seen from the figure, the pure zinc oxide nano material prepared in the comparative example 1 and the CQDs @ ZnO composite nano material prepared in the examples 1-3 are both spherical, and the particle size ranges from 3 nm to 5 nm. But compared with a pure zinc oxide nano material, the CQDs @ ZnO composite nano material has the advantages of reduced agglomeration, better monodispersity and increased stability in methanol.
FIG. 2 shows the UV-VIS absorption spectra of the zinc oxide nanomaterial prepared in comparative example 1 and the CQDs @ ZnO composite nanomaterials prepared in examples 1-3. As can be seen from the figure, the absorption range of the pure zinc oxide nano material without the carbon quantum dots reaches 360nm, the light absorption cut-off wavelength of the CQDs @ ZnO composite nano material with different carbon quantum dot doping amounts has obvious blue shift, and the blue shift phenomenon is more obvious along with the increase of the carbon quantum dot doping amount. This indicates that the band gap of the synthesized CQDs @ ZnO composite nano-material structure is increased.
FIG. 3 shows photoluminescence spectra of zinc oxide nanomaterial prepared in comparative example 1 and CQDs @ ZnO composite nanomaterial prepared in examples 1-3. As can be seen from the figure, all the nano materials have two intrinsic emission peaks in the range of 400-440 nm, and have a broad peak in the range of 480-640 nm, and the broad peak corresponds to a zinc oxide surface defect peak. It can be seen from the figure that after the carbon quantum dots are introduced, the corresponding defect peak at 560nm is greatly reduced, suggesting that the introduction of the carbon quantum dots effectively inhibits the surface and internal defects of the zinc oxide.
FIG. 4 shows the X-ray diffraction patterns of the zinc oxide nanomaterial prepared in comparative example 1 and the CQDs @ ZnO composite nanomaterials prepared in examples 1 and 3. As can be seen from the figure, all samples show standard diffraction peaks of zinc oxide, and obvious diffraction peaks at 2 θ of 31 °, 35 °, 47 °, 56 °, 62 ° and 67 ° respectively correspond to (100), (002), (101), (102), (110) and (103) crystal planes of the hexagonal wurtzite crystal form ZnO. It can be seen that after the introduction of the carbon quantum dots, the composite material mainly exhibits the standard hexagonal wurtzite zinc oxide structure. It can also be seen that the crystallinity of zinc oxide decreases with increasing incorporation of carbon quantum dots.
Example 4.
0.011g of carbon quantum dots are weighed and added into 10mL of anhydrous methanol, and ultrasonic dispersion is carried out for 5 min.
0.74g of potassium hydroxide was weighed, added to 23mL of anhydrous methanol, and dissolved for 5min with ultrasound.
And mixing the prepared carbon quantum dot methanol dispersion liquid with a potassium hydroxide methanol solution, and performing ultrasonic dispersion.
Weighing 1.475g of zinc acetate, adding the zinc acetate into 63mL of anhydrous methanol, heating to 63 ℃ under stirring, keeping the temperature, and dropwise adding the mixed solution of the potassium hydroxide and the methanol with the carbon quantum dots at a constant speed within 9 min.
After the methanol mixed solution is dripped, the temperature is kept and the stirring is continued, white precipitate is generated after 9min, the solution becomes clear after 11min, and precipitate is generated again after 1 h. After 1.5h, the heating and stirring were stopped, and after standing for 4h, the product settled completely.
And (3) discarding the supernatant, washing the product with anhydrous methanol for 2 times, and centrifuging to obtain the CQDs @ ZnO composite nano material with the carbon quantum dot content of 2%.
Example 5.
0.0055g of carbon quantum dots was weighed, added to 10mL of anhydrous methanol, and ultrasonically dispersed for 5 min.
0.74g of potassium hydroxide was weighed, added to 23mL of anhydrous methanol, and dissolved for 5min with ultrasound.
And mixing the prepared carbon quantum dot methanol dispersion liquid with a potassium hydroxide methanol solution, and performing ultrasonic dispersion.
Weighing 1.475g of zinc acetate, adding the zinc acetate into 63mL of anhydrous methanol, heating to 63 ℃ under stirring, keeping the temperature, and dropwise adding the mixed solution of the potassium hydroxide and the methanol with the carbon quantum dots at a constant speed within 10 min.
After the methanol mixed solution is dripped, the temperature is kept and the stirring is continued, white precipitate is generated after 10min, the solution becomes clear after 14min, and precipitate is generated again after 1.1 h. After 1.5h, the heating and stirring were stopped, and after standing for 4h, the product settled completely.
And (3) discarding the supernatant, washing the product with anhydrous methanol for 2 times, and centrifuging to obtain the CQDs @ ZnO composite nano material with the carbon quantum dot content of 1%.
Example 6.
The CQDs @ ZnO composite nano material prepared in the embodiment 1 of the invention is used as a cathode interface layer material, and the structure of a prepared device is ITO/CQDs @ ZnO/PM6: IT-4F/MoO3Al organic solar cell.
The organic solar cell prepared in this embodiment has a six-layer structure, in which the first layer is a conductive transparent glass layer, the second layer is a cathode layer, i.e., an ITO layer, the third layer is a cathode interface layer, i.e., a CQDs @ ZnO composite nanomaterial layer, the fourth layer is an organic active layer, the fifth layer is an anode interface layer, i.e., a molybdenum oxide layer, and the sixth layer is an anode layer, i.e., an aluminum layer. The process for preparing the organic solar cell is a traditional process and has no special requirements.
Placing ITO glass with the specification of 25mm multiplied by 1mm multiplied by 25mm in a polytetrafluoroethylene bracket, and sequentially placing the ITO glass in deionized water, absolute ethyl alcohol, acetone and isopropanol for ultrasonic cleaning.
And removing isopropanol on the surface of the cleaned ITO glass by using high-speed nitrogen, placing the cleaned ITO glass in a closed ultraviolet irradiation box, and irradiating for 30min at the irradiation power of 50W.
The CQDs @ ZnO composite nanomaterial prepared in example 1 is added into absolute methanol for ultrasonic treatment to obtain a uniform dispersion liquid, and the uniform dispersion liquid is diluted into CQDs @ ZnO composite nanomaterial dispersion liquid of 10 mg/mL.
Placing the ITO glass on a spin coater, dropwise adding 0.1mL of CQDs @ ZnO composite nano material dispersion liquid, closing and starting the spin coater, starting a vacuum pump to enable the vacuum degree in the spin coater to reach 2Pa, and spin-coating for 60s at a rotating speed of 3000 r/min. And after the spin coating is finished, placing the ITO glass on a pre-opened hot table, annealing for 10min at 125 ℃, and spin coating on the ITO glass to obtain a cathode interface layer.
Weighing 0.003g of PM6 and 0.003g of IT-4F, adding into 0.3mL of chlorobenzene, mixing, stirring for 4 hours at 50 ℃, adding 1.5 mu m 1, 8-diiodooctane, and stirring for 30 minutes to prepare an organic active layer solution.
And placing the ITO glass on a spin coater, adding 40 mu L of organic active layer solution on the surface of the cathode interface layer, sealing the spin coater, starting a vacuum pump to enable the vacuum degree in the spin coater to reach 1Pa, and spin-coating for 60s at the rotating speed of 2200 r/min. And taking out the ITO glass, placing the ITO glass on a pre-opened hot bench, and annealing at 150 ℃ for 15min to obtain the organic active layer.
The ITO glass coated with the organic active layer in a spinning mode is placed on a turntable at the top of a vacuum evaporation instrument, and 1g of molybdenum oxide is weighed and placed on a target table at the bottom of the vacuum evaporation instrument. Sealing the vacuum evaporation apparatus, starting the mechanical pump, and when the pressure in the evaporation apparatus is reduced to 0Pa, starting the molecular pump to reduce the pressure in the apparatus to 5 × 10-4And Pa, starting a turntable at the top of the vacuum evaporation instrument, rotating at the speed of 15r/min, starting a heating instrument at the bottom of the vacuum evaporation instrument, and evaporating molybdenum oxide when the temperature is constant to 350 ℃ for 15 min.
And closing the bottom heating device and the top rotating device of the vacuum evaporation instrument, opening the vacuum evaporation instrument, and placing 1g of aluminum on a target table at the bottom of the vacuum evaporation instrument. And repeating the operation, opening a heating instrument at the bottom of the vacuum evaporation instrument, starting to evaporate aluminum when the temperature is constant at 900 ℃, wherein the evaporation time is 20min, and then closing the evaporation instrument.
And taking out the ITO glass from the evaporation instrument to prepare the organic solar cell V1.
Example 7.
In the same manner as in example 6 except that the CQDs @ ZnO composite nanomaterial prepared in example 2 was used, the device structure was prepared as ITO/CQDs @ ZnO/PM6: IT-4F/MoO3Al organic solar cell V2.
Example 8.
In the same manner as in example 6 except that the CQDs @ ZnO composite nanomaterial prepared in example 3 was used, the device structure was prepared as ITO/CQDs @ ZnO/PM6: IT-4F/MoO3The organic solar cell device V3 of/Al.
Comparative example 2.
Oxidation as prepared in comparative example 1The zinc nano material replaces CQDs @ ZnO composite nano material, and the other steps are the same as those of the embodiment 6, and the prepared device has the structure of ITO/ZnO/PM6, IT-4F/MoO3The organic solar cell device V0 of/Al.
Fig. 5 is a graph of current density versus voltage characteristics of the organic solar cells V0, V1, V2, V3. The bias voltage scan during the battery test is-0.1 to 1V.
As can be seen from the figure, the organic solar cell V2 has higher open-circuit voltage, short-circuit current and higher fill factor, and the final cell efficiency is improved by 7.17% compared with V0.
Fig. 6 is a graph of external quantum efficiency for devices V0, V1, V2, V3. As shown in the figure, the organic solar cell has strong photoelectric response in the range of 320-680 nm. In the range of 420-520 nm, V1, V2 and V3 have stronger photoelectric responses than V0, which is attributed to the absorption of carbon quantum dots in this range.
The statistical results of the performances of the organic solar cells with different cathode interface layer materials are shown in table 1.
Figure 555868DEST_PATH_IMAGE001
As shown in Table 1, when the doping amount of the carbon quantum dots is 2%, the photoelectric conversion efficiency of the organic solar cell is the highest and reaches 12.11%, the corresponding open-circuit voltage is 0.83V, and the short-circuit current is 20.75mA/cm2The filling factor is 0.71, which is far superior to 11.30% of photoelectric conversion efficiency of the organic solar cell prepared from zinc oxide without doping carbon quantum dots.
Example 9.
ITO glass was prepared by washing according to the method of example 6.
The CQDs @ ZnO composite nanomaterial prepared in example 1 is added into absolute methanol for ultrasonic treatment to obtain a uniform dispersion liquid, and the uniform dispersion liquid is diluted into CQDs @ ZnO composite nanomaterial dispersion liquid of 10 mg/mL.
According to the method of the embodiment 6, a CQDs @ ZnO composite nano material cathode interface layer is spin-coated on the ITO glass.
0.01g P3HT, 0.012g bis-PCBM was weighed and mixed with 0.5mL dichlorobenzene, and stirred at 40 ℃ for 10 hours to prepare an organic active layer solution.
And placing the ITO glass on a spin coater, adding 40 mu L of organic active layer solution on the surface of the cathode interface layer, sealing the spin coater, starting a vacuum pump to enable the vacuum degree in the spin coater to reach 1Pa, and spin-coating for 60s at the rotating speed of 2200 r/min. And (3) taking out the ITO glass from the spin coater, placing the ITO glass in a culture dish, annealing with dichlorobenzene at 25 ℃ for 2h, taking out the ITO glass, placing the ITO glass on a pre-opened hot bench, and annealing at 160 ℃ for 10min to obtain the organic active layer.
Continuing to prepare a molybdenum oxide anode interface layer and an aluminum anode layer on the organic active layer by evaporation according to the method of the embodiment 6, and obtaining the device with the structure of ITO/CQDs @ ZnO/P3HT: bis-PCBM/MoO3The organic solar cell device V4 of/Al.
Example 10.
In the same manner as in example 9 except that the CQDs @ ZnO composite nanomaterial prepared in example 2 was used, the device structure was prepared as ITO/CQDs @ ZnO/P3HT: bis-PCBM/MoO3The organic solar cell device V5 of/Al.
Example 11.
In the same manner as in example 9 except that the CQDs @ ZnO composite nanomaterial prepared in example 3 was used, the device structure was prepared as ITO/CQDs @ ZnO/P3HT: bis-PCBM/MoO3The organic solar cell device V6 of/Al.
Comparative example 3.
The zinc oxide nano material prepared in the comparative example 1 replaces CQDs @ ZnO composite nano material, and the structure of the device prepared in the other same example 9 is ITO/ZnO/P3HT: bis-PCBM/MoO3The organic solar cell device V00 of/Al.
Fig. 7 and 8 show graphs of current density and voltage characteristics of the organic solar cell devices V00, V4, V5 and V6, respectively, and corresponding graphs of external quantum efficiency.
As can be seen from the figure, the organic solar cell device V5 has a higher fill factor. The cell has strong photoelectric response in the range of 320-850 nm. In the 400-600 nm range, V4, V5 and V6 have stronger photoelectric response compared with V00, which is attributed to the absorption of carbon quantum dots in the range.
The statistical results of the performance of the organic solar cell devices prepared by different cathode interface layer materials are given in table 2.
Figure 849315DEST_PATH_IMAGE002
As shown in Table 2, when the doping amount of the carbon quantum dots is 1%, the device performance of the organic solar cell is optimal, the photoelectric conversion efficiency reaches 4.64%, the corresponding open-circuit voltage is 0.73V, and the short-circuit current is 9.63mA/cm2The filling factor is 0.66, which is far superior to the photoelectric conversion efficiency of the organic solar cell 4.13 prepared by zinc oxide without doping carbon quantum dots.
The comparative examples 2 and 3 prove that the CQDs @ ZnO composite nano material can obviously improve the surface and internal defects of a pure zinc oxide nano material when used as a cathode interface layer in organic solar cells with different active layer materials.
The names and chemical structural formulas of specific compounds corresponding to the abbreviations of the organic active layer chemical substances in the above-described embodiments of the present invention are as follows.
P3HT：poly(3-hexylthiophene)。
Figure 857722DEST_PATH_IMAGE003
bis-PCBM：bisadduct of phenyl-C61-butyric acid methyl ester。
Figure 333965DEST_PATH_IMAGE004
PM6：Poly[(2,6-(4,8-bis(5-(2-ethylhexyl-3-fluoro)thiophen-2-yl)-benzo[1,2-b:4,5-b']dithiophene))-alt-(5,5-(1',3'-di-2-thienyl-5',7'-bis(2-ethylhexyl)benzo[1',2'-c:4',5'-c']dithiophene-4,8-dione)]。
Figure 908166DEST_PATH_IMAGE005
IT-4F：3,9-bis(2-methylene-((3-(1,1-dicyanomethylene)-6,7-difluoro)-indanone))-5,5,11,11-tetrakis(4-hexylphenyl)-dithieno[2,3-d:2',3'-d']-s-indaceno[1,2-b:5,6-b']dithiophene。
Figure 326509DEST_PATH_IMAGE006

Claims (8)

1. A carbon quantum dot @ zinc oxide composite nano material is prepared by adding a carbon quantum dot and an anhydrous methanol mixed solution of potassium hydroxide into an anhydrous methanol solution of zinc acetate to react by adopting an in-situ synthesis method.
2. The carbon quantum dot @ zinc oxide composite nanomaterial according to claim 1, wherein the mass ratio of the carbon quantum dots to the zinc oxide is 0.1-20: 100.
3. The carbon quantum dot @ zinc oxide composite nanomaterial according to claim 1, wherein the mass ratio of the carbon quantum dots to the zinc oxide is 0.5-5: 100.
4. The preparation method of the carbon quantum dot @ zinc oxide composite nanomaterial as claimed in claim 1, wherein the carbon quantum dot is dispersed in anhydrous methanol, a potassium hydroxide anhydrous methanol solution is added to obtain a methanol mixed solution of potassium hydroxide and the carbon quantum dot, the methanol mixed solution is dropwise added into a zinc acetate anhydrous methanol solution heated to 62-64 ℃ to react, the mixture is kept stand to precipitate, and the precipitate is washed and dried to obtain the carbon quantum dot @ zinc oxide composite nanomaterial.
5. The preparation method of the carbon quantum dot @ zinc oxide composite nanomaterial according to claim 4, characterized in that the reaction is carried out at 62-64 ℃ under stirring for not less than 1.5 hours.
6. The method for preparing the carbon quantum dot @ zinc oxide composite nanomaterial according to claim 4, wherein the standing time is not less than 4 hours.
7. The preparation method of the carbon quantum dot @ zinc oxide composite nanomaterial as claimed in claim 4, wherein the carbon quantum dot is ultrasonically dispersed in anhydrous methanol, potassium hydroxide is ultrasonically dissolved in anhydrous methanol, and the carbon quantum dot methanol dispersion liquid is mixed with a potassium hydroxide methanol solution, and the methanol mixture of potassium hydroxide and the carbon quantum dot is obtained by ultrasonic dispersion.
8. The application of the carbon quantum dot @ zinc oxide composite nanomaterial as defined in any one of claims 1 to 3 as a cathode interface layer material of an organic solar cell.
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