CN109326672B - Preparation method of solar fluorescent light collector based on all-inorganic perovskite quantum dots - Google Patents
Preparation method of solar fluorescent light collector based on all-inorganic perovskite quantum dots Download PDFInfo
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- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/054—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means
- H01L31/055—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means where light is absorbed and re-emitted at a different wavelength by the optical element directly associated or integrated with the PV cell, e.g. by using luminescent material, fluorescent concentrators or up-conversion arrangements
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention relates to a preparation method of a solar fluorescent light collector based on all-inorganic perovskite quantum dots, and belongs to the technical field of photoelectric luminescence. The preparation method comprises the following steps: s1, injecting the cesium-oleic acid mixed solution into lead halide precursor liquid through a thermal injection method to prepare halogen-doped all-inorganic perovskite quantum dots; s2, dissolving all-inorganic perovskite quantum dots and a photoinitiator in an allyl monomer, mixing the allyl monomer with a thiol monomer to form a mixed solution, carrying out ultrasonic treatment on the mixed solution for 0.5-1.5min, pouring the mixed solution into a mold, carrying out drying treatment in a vacuum environment for 25-35min, then carrying out curing by adopting ultraviolet lamp irradiation, curing and demolding, and then carrying out cutting and polishing processes to obtain the all-inorganic perovskite quantum dot-based solar fluorescent light collector. The solar fluorescent light collector prepared by the invention is green and environment-friendly, and has good mechanical property; the spectrum absorption range is wide and adjustable, and the solar photovoltaic cell can be suitable for various solar photovoltaic cells; the light collecting efficiency is high.
Description
Technical Field
The invention belongs to the technical field of photoelectric luminescence, and relates to a preparation method of a solar fluorescent light collector based on all-inorganic perovskite quantum dots.
Background
The solar energy collection system comprises a photovoltaic power generation assembly, a solar light collector, a fluorescent light waveguide panel, a solar energy collector, a fluorescent light waveguide panel, a fluorescent light waveguide board, a solar energy collector, a fluorescent light waveguide board, a fluorescent light reflector, a fluorescent light waveguide board, a fluorescent light reflector, a fluorescent light waveguide, a fluorescent light reflector, a fluorescent light.
The technical bottleneck for limiting the improvement of the photon collection efficiency of the fluorescent solar light collector is that the reabsorption probability in the photon transmission process is reduced and the surface escape rate of photons is reduced.
Disclosure of Invention
The invention aims to provide a preparation method of a solar fluorescence light collector based on all-inorganic perovskite quantum dots, aiming at the technical problems of high reabsorption rate, high photon escape probability, low light collection efficiency and the like in the conventional solar fluorescence light collector, the prepared solar fluorescence light collector can effectively reduce reabsorption probability and photon escape probability of a luminescence center in a photon transportation process, has high light collection efficiency, and has the light collection efficiency of a solar fluorescence light collection prototype device based on all-inorganic perovskite quantum dots larger than 5 percent through preliminary tests.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of a solar fluorescence light collector based on all-inorganic perovskite quantum dots comprises the following steps,
s1, preparing all-inorganic perovskite quantum dots: injecting the cesium-oleic acid mixed solution into lead halide precursor liquid by a thermal injection method to prepare halogen-doped all-inorganic perovskite quantum dots;
s2, preparation of the solar fluorescent light collector: dissolving all-inorganic perovskite quantum dots and a photoinitiator in an allyl monomer, mixing the allyl monomer with a thiol monomer, performing ultrasonic treatment for 0.5-1.5min, pouring the mixture into a mold, performing drying treatment for 25-35min in a vacuum environment, heating at a constant temperature of 65-75 ℃ for 25-35min, and then irradiating by using an ultraviolet lamp for curing. And after curing and demolding, cutting and polishing to obtain the solar fluorescent light collector based on the all-inorganic perovskite quantum dots.
The thiol-ene copolymer (OSTE) is used as a photon transport matrix material of the solar collector, and the all-inorganic perovskite quantum dots doped with various halogens are used as a luminescent center material of the solar collector, so that the preparation of the solar fluorescent light-collecting prototype device with higher light-collecting efficiency is realized. The reason for the high light collection efficiency of the prototype device is the following four aspects: firstly, compared with the traditional polymer matrix materials such as PMMA, PDMS and the like, OSTE has higher theoretical refractive index (more than 1.7), and the larger total reflection angle can effectively reduce the photon escape rate in the solar fluorescent light collection prototype device; secondly, compared with the existing luminescent center materials such as CdS, Si, CIGS and InP quantum dots, the all-inorganic perovskite quantum dot has higher fluorescence quantum yield (more than 50 percent) and larger Stokes shift, and the excellent spectroscopic property can effectively reduce the photon reabsorption probability in the solar fluorescent light collecting primitive device; thirdly, the halogen is doped with the all-inorganic perovskite quantum dot, so that the light-emitting function of the all-inorganic perovskite quantum dot is realized, and the all-inorganic perovskite quantum dot has good luminous stability and monochromaticity; fourthly, compared with the existing luminescent organic dye molecules such as Coumarin, Rhodamine and the like, the halogen-doped all-inorganic perovskite quantum dot has better luminescent stability and monochromaticity. Compared with the traditional toxic substances such as CdS quantum dots and the like, the all-inorganic perovskite quantum adopted by the invention is more environment-friendly; compared with traditional CIGS quantum dots and other luminescent centers, the cost is lower.
The method comprises the steps of adding different halogen-doped all-inorganic perovskite quantum dots into a polymer monomer material, and then adopting the processes of ultrasonic treatment, constant-temperature heating, vacuum drying, ultraviolet curing, demoulding, polishing and the like to fully dissolve and uniformly disperse the all-inorganic perovskite quantum dots into the polymer monomer material.
Preferably, the cesium-oleic acid in step S1The mixed solution is prepared by mixing Oleic Acid (OA) and cesium titanate (Cs)2CO3) Adding into Octadecene (ODE), stirring and heating to 190-210 ℃ until the white powder is completely dissolved, and then preserving the temperature for 0.8-1.2h at the temperature of 125-135 ℃ in a vacuum environment to prepare the cesium-oleic acid mixed solution.
Preferably, in the step S1, during the preparation of the cesium-oleic acid mixed solution, the OA and Cs are2CO3The addition amount of ODE is calculated according to the following proportion: every 1g of Cs2CO3The mixture ratio of OA is 2.6-3.4mL and ODE is 45-55 mL.
Preferably, the cesium-oleic acid mixed solution in the step S1 is kept at a temperature of not less than 80 ℃ to avoid precipitation.
Preferably, the preparation process of the lead halide precursor liquid in the step S1 is as follows: mixing OA, Oleylamine (OLA), ODE and lead halide (PbX)2) Mixing the solid powders, and treating at 90-110 deg.C for 25-35min in vacuum environment to obtain lead halide precursor solution, OA, OLA, ODE and PbX2The addition amount of the solid powder is calculated according to the following proportion: 0.35-0.40mmol of PbX per unit2The solid powder was prepared from 1ml OA, 1ml OLA and 10ml ODE.
Preferably, PbX is used in the step S12Is PbCl2、PbBr2、PbI2(i.e. PbX)2Wherein X ═ Cl, Br, I).
Preferably, PbX is used in the step S12Is PbCl2、PbBr2、PbI2Two or three of them.
Compared with a single halogen-doped all-inorganic perovskite quantum dot and other luminescent center materials, the multiple halogen-doped all-inorganic quantum dots have wider spectral absorption range (up to 400nm to 700 nm). According to the invention, two or three lead halides are compounded in a specific ratio, so that the accurate adjustment of the luminescence peak position of the inorganic perovskite quantum dot can be realized, and the adjustable luminescence peak position is more easily applied to various optimal response spectrums of commercial photovoltaic devices based on different semiconductor materials, so that the light collector disclosed by the invention can be applied to various different solar photovoltaic cells; meanwhile, different halogen dopings have a synergistic effect, so that the light collecting efficiency of the light collector can be further improved.
Preferably, the lead halide precursor solution is stored in N2In the environment.
Preferably, the specific process of the thermal injection method in the step S1 is to heat the lead halide precursor liquid to 125-.
Preferably, the cesium-oleic acid solution is injected into the lead halide precursor liquid in the step S1 in a proportion calculated according to a molar ratio of Cs to Pb of 1 (1-1.5).
Preferably, the halogen-doped all-inorganic perovskite quantum dots prepared in the step S1 are stored in a vacuum drier or a refrigerator at-10 ℃.
The fully inorganic perovskite quantum dot prepared by the method is very sensitive to humidity, and needs to be stored in a drier or a refrigerator at the temperature of-10 ℃ in order to avoid deterioration caused by contact with water molecules in the air environment.
Preferably, the concentration of the all-inorganic perovskite quantum dots in the mixed solution of step S2 is 10-7-10-4mol/L。
Preferably, the contents of the photoinitiator, the allyl monomer and the thiol monomer in the mixed solution of step S2 are calculated according to the following ratio, and the ratio of the allyl monomer to the thiol monomer is 80-120mL to 80-120mL per 1g of the photoinitiator.
Preferably, the photoinitiator in step S2 is 1-hydroxycyclohexyl phenyl ketone, the propyl monomer is triallyl-1, 3, 5-triazine-2, 4,6(1H, 3H, 5H) -trione, and the thiol monomer is pentaerythritol tetrakis (3-mercaptopropionate).
Preferably, the mold in step S2 is a Teflon mold.
Preferably, the preparation method further comprises a step of mold pretreatment, and specifically, before the solar fluorescent light collector is prepared, the mold is sequentially subjected to ultrasonic cleaning, absolute ethyl alcohol treatment and absorbent paper wiping until the surface of the mold is dried.
Preferably, the drying process in step S2 is performed in a vacuum atmosphere of not more than 133 Pa.
Preferably, the constant temperature heating in step S2 is water bath heating.
Preferably, in step S2, the power of the uv light is not lower than 50W, the central wavelength is 365nm, and the irradiation time is 8-12S.
Compared with the prior art, the invention has the following beneficial effects: the solar fluorescent light collector prepared by the invention is green and environment-friendly, and has good mechanical property; the spectrum absorption range is wide and adjustable, and the solar photovoltaic cell can be suitable for various solar photovoltaic cells; the light collecting efficiency is high.
Drawings
FIG. 1 shows a diagram of a fully inorganic perovskite CsPbBr prepared by a thermal injection method in example 1 of the present invention3A transmission electron microscope image (a), a size distribution statistical image (b), and a high-resolution transmission electron microscope image (c) of the quantum dots.
Fig. 2 shows fluorescence emission spectra (a) and absorption spectra (b) of different halogen all-inorganic perovskite quantum dots prepared in example 1, example 2 and example 3 of the present invention.
Fig. 3 is a fluorescence emission spectrum of a plurality of halogen composite doped all-inorganic perovskite quantum dots prepared in example 4 of the invention.
Fig. 4 shows the variation of the reabsorption loss (a), the reemission loss (b), the photon escape loss (c) and the light collection efficiency (d) of the solar fluorescent light collector based on the all-inorganic perovskite quantum dots prepared in example 1 of the present invention with the doping concentration of the quantum dots.
Detailed Description
The following are specific examples of the present invention and further describe the technical solutions of the present invention, but the present invention is not limited to these examples.
Example 1
The preparation method of the perovskite quantum dot-based solar fluorescent light collector in the embodiment comprises the following steps,
(1) preparation of cesium-oleic acid mixed solution: 0.6mL OA and 0.2g Cs2CO3Adding into 9.8mL ODE, stirring and heating to 200 deg.C until white powder is completely dissolved, then maintaining at 130 deg.C for 1.0h in vacuum environment to obtain cesium-oleic acid mixed solution, and storing the obtained cesium-oleic acid mixed solution at a temperature not lower than 80 deg.C to avoid precipitation.
(2) Preparing a lead halide precursor solution: 1mL OA, 1mL OLA, 10mL ODE and 0.376mmol PbBr2Adding solid powder into 100mL round bottom flask, placing in vacuum environment, holding at 100 deg.C for 30min to obtain lead halide precursor solution, wherein OLA solution and OA solution are injected rapidly at 100 deg.C in nitrogen atmosphere, storing the obtained lead halide precursor solution in N2In the environment.
(3) Preparing all-inorganic perovskite quantum dots: heating lead halide precursor liquid to 130 ℃ in a vacuum environment, preserving heat for 30min, then heating to 160 ℃, then quickly injecting cesium-oleic acid solution to ensure that the molar ratio of Cs to Pb of the cesium-oleic acid solution is 1:1, keeping the temperature at 160 ℃ for 5min, and then quickly cooling in a water bath to obtain CsPbBr3And (3) storing the quantum dots, namely the prepared all-inorganic perovskite quantum dots in a vacuum drier or a refrigerator at the temperature of-10 ℃.
(4) Preparing a solar fluorescent light collector: sequentially carrying out ultrasonic cleaning, absolute ethyl alcohol treatment and water absorption paper wiping on the Teflon mould until the surface of the mould is dried; reacting CsPbBr3Quantum dots and 0.02g photoinitiator (1-hydroxycyclohexyl phenyl ketone, Irgacure-184) were dissolved in 2mL of allyl monomer (triallyl-1, 3, 5-triazine-2, 4,6(1H, 3H, 5H) -trione) and mixed with 2mL of thiol monomer (pentaerythritol tetrakis (3-mercaptopropionate)) to form a mixture, and CsPbBr was added3The concentration of the quantum dots in the mixed solution is 2.1 multiplied by 10-5And mol/L, pouring the mixed solution into a Teflon mold after ultrasonic treatment for 1min, drying the mixed solution for 30min in a vacuum environment with the pressure of not higher than 133Pa, heating the mixed solution for 30min at a constant water bath temperature of 70 ℃, curing the mixed solution by ultraviolet light irradiation with the irradiation power of 100W, the central wavelength of 365nm and the irradiation time of 10s, and finally performing polishing process after curing and demolding to obtain the solar fluorescent light collector.
Example 2
PbX2Is PbCl2Otherwise, the same as in example 1.
Example 3
PbX2Is PbI2Otherwise, the same as in example 1.
Example 4
PbX2Is PbCl2、PbBr2、PbI2A mixture of two or three of (A), PbCl2、PbBr2、PbI2The molar ratio of (0-1) to (0-1) was the same as in example 1.
Example 5
The preparation method of the perovskite quantum dot-based solar fluorescent light collector in the embodiment comprises the following steps,
(1) preparation of cesium-oleic acid mixed solution: 0.5mL OA and 0.2g Cs2CO3Adding into 9.0mL ODE, stirring and heating to 190 deg.C until white powder is completely dissolved, then maintaining at 125 deg.C for 0.8h in vacuum environment to obtain cesium-oleic acid mixed solution, and storing the obtained cesium-oleic acid mixed solution at a temperature of not lower than 80 deg.C to avoid precipitation.
(2) Preparing a lead halide precursor solution: 1mL OA, 1mL OLA, 10mL ODE and 0.35mmol PbBr2Adding solid powder into 50mL round bottom flask, placing in vacuum environment, holding at 90 deg.C for 30min to obtain lead halide precursor solution, wherein OLA solution and OA solution are injected rapidly at 90 deg.C in nitrogen atmosphere, storing the obtained lead halide precursor solution in N2In the environment.
(3) Preparing all-inorganic perovskite quantum dots: heating the lead halide precursor liquid to 125 ℃ in a vacuum environment, preserving heat for 25min, then heating to 155 ℃, then quickly injecting a cesium-oleic acid solution to ensure that the molar ratio of Cs to Pb of the cesium-oleic acid solution is 1:1, keeping the temperature at 155 ℃ for 4min, and then quickly cooling in a water bath to obtain CsPbBr3And (3) storing the quantum dots, namely the prepared all-inorganic perovskite quantum dots in a vacuum drier or a refrigerator at the temperature of-10 ℃.
(4) Preparing a solar fluorescent light collector: sequentially carrying out ultrasonic cleaning, absolute ethyl alcohol treatment and water absorption paper wiping on the Teflon mould until the Teflon mould is cleanedSurface drying; reacting CsPbBr3Quantum dots and 0.02g photoinitiator (1-hydroxycyclohexyl phenyl ketone, Irgacure-184) were dissolved in 1.6mL allyl monomer (triallyl-1, 3, 5-triazine-2, 4,6(1H, 3H, 5H) -trione) and mixed with 2.4mL thiol monomer (pentaerythritol tetrakis (3-mercaptopropionate)) to form a mixture, CsPbBr was added3The concentration of the quantum dots in the mixed solution is 2.1 multiplied by 10-7And mol/L, pouring the mixed solution into a Teflon mold after ultrasonic treatment for 0.5min, drying the mixed solution for 30min in a vacuum environment with the pressure of not higher than 133Pa, heating the mixed solution for 25min in a water bath at the constant temperature of 65 ℃, curing the mixed solution by ultraviolet light irradiation with the irradiation power of 130W and the central wavelength of 365nm for 8s, and finally performing a polishing process after curing and demolding to obtain the solar fluorescent light collector.
Example 6
The preparation method of the perovskite quantum dot-based solar fluorescent light collector in the embodiment comprises the following steps,
(1) preparation of cesium-oleic acid mixed solution: 0.68mL of OA and 0.2g of Cs2CO3Adding into 11mL ODE, stirring and heating to 210 deg.C until white powder is completely dissolved, and maintaining at 135 deg.C for 1.2h in vacuum environment to obtain cesium-oleic acid mixed solution, and storing the obtained cesium-oleic acid mixed solution at a temperature of not lower than 80 deg.C to avoid precipitation.
(2) Preparing a lead halide precursor solution: 1mL OA, 1mL OLA, 10mL ODE and 0.40mmol PbBr2Adding solid powder into 50mL round bottom flask, placing in vacuum environment, holding at 110 deg.C for 35min to obtain lead halide precursor solution, wherein OLA solution and OA solution are injected rapidly at 110 deg.C in nitrogen atmosphere, storing the obtained lead halide precursor solution in N2In the environment.
(3) Preparing all-inorganic perovskite quantum dots: heating lead halide precursor liquid to 135 ℃ in a vacuum environment, preserving heat for 35min, then heating to 165 ℃, then quickly injecting cesium-oleic acid solution to ensure that the molar ratio of Cs to Pb of the cesium-oleic acid solution is 1:1.5, keeping the temperature at 165 ℃ for 6min, and then quickly cooling in a water bath to obtain CsPbBr3Quantum dot and prepared all-inorganic perovskite quantum dotStored in a desiccator or in a-10 ℃ refrigerator.
(4) Preparing a solar fluorescent light collector: sequentially carrying out ultrasonic cleaning, absolute ethyl alcohol treatment and water absorption paper wiping on the Teflon mould until the surface of the mould is dried; reacting CsPbBr3Quantum dots and 0.02g photoinitiator (1-hydroxycyclohexyl phenyl ketone, Irgacure-184) were dissolved in 2.4mL of allyl monomer (triallyl-1, 3, 5-triazine-2, 4,6(1H, 3H, 5H) -trione) and mixed with 1.6mL of thiol monomer (pentaerythritol tetrakis (3-mercaptopropionate)) to form a mixture, and CsPbBr was added3The concentration of the quantum dots in the mixed solution is 10-4And mol/L, pouring the mixed solution into a Teflon mold after ultrasonic treatment for 1.5min, drying for 35min in a vacuum environment of not more than 133Pa, heating at a constant water bath temperature of 75 ℃ for 35min, curing by ultraviolet irradiation with the irradiation power of an ultraviolet lamp of 150W, the central wavelength of 365nm and the irradiation time of 12s, and finally performing polishing after curing and demolding to obtain the solar fluorescent light collector.
The solar fluorescent light collector prepared in the embodiment of the invention is a solar fluorescent prototype device, and for the convenience of detection, the size of the solar fluorescent light collector prepared in the embodiment of the invention is 6.0cm × 6.0cm × 0.3cm (length × width × thickness).
The invention carries out a series of optical tests and characterizations on the all-inorganic perovskite quantum dots and the solar fluorescence light collector prepared in the embodiment, and the test method and the results are as follows:
the structural characterization of the all-inorganic perovskite quantum dots is carried out by adopting a Techni F20 field emission high-resolution transmission electron microscope (HR-TEM) of FEI company in America; the steady state fluorescence emission (PL) spectrum of the all-inorganic perovskite quantum dot adopts a Fluorolo-3 fluorescence test system produced by Jobin Yvon France, and an excitation light source is a 30mW He-Cd light collector (the central wavelength is 325 nm); the visible detector employs a photomultiplier tube (PMT) model R928 from Hamamatsu corporation of Japan; the absorption spectrum test of the all-inorganic perovskite quantum dot adopts a UV3600 ultraviolet visible near-infrared spectrophotometer of Shimadzu corporation of Japan; external quantum yield testing of all-inorganic perovskite quantum dots employs Quantaurus-QY Plus test system from Hamamatsu, japan. All the fluorescence signals tested in the invention are corrected according to the instrument parameters, and the environmental noise is deducted.
FIG. 1 shows a diagram of a fully inorganic perovskite CsPbBr prepared by a thermal injection method in example 1 of the present invention3A transmission electron microscope image (a), a size distribution statistical image (b), and a high-resolution transmission electron microscope image (c) of the quantum dots. The test was carried out using a Technai F20 field emission transmission electron microscope (FEI, USA) with an acceleration voltage of 200 kV.
As seen in FIG. 1(a), CsPbBr3The quantum dots are uniformly distributed and have uniform size. As shown in FIG. 1(b), CsPbBr was counted according to the image processing software ImageJ3The average size of the quantum dots is 8.4 +/-2.8 nm. FIG. 1(c) shows high resolution CsPbBr of all-inorganic perovskite3As can be seen from FIG. 1(c), a transmission electron microscope photograph of the quantum dots, CsPbBr was prepared3The interplanar spacing of the quantum dots was 0.58nm, corresponding to a cubic CsPbBr3The (001) plane of the quantum dot. The high-resolution TEM picture further proves that the inorganic perovskite CsPbBr with uniform size and typical cubic structure3And (4) synthesis of quantum dots.
Fig. 2 shows fluorescence emission spectra (a) and absorption spectra (b) of different halogen all-inorganic perovskite quantum dots prepared in example 1, example 2 and example 3 of the present invention. As seen from fig. 2(a), the different halogen all-inorganic perovskite quantum dots all exhibit good luminescence monochromaticity (about 20nm of luminescence full width at half maximum) and high fluorescence quantum yield (> 50%). As seen from fig. 2(b), the different halogen all-inorganic perovskite quantum dots exhibit a broad absorption spectral range.
FIG. 3 shows fluorescence emission spectra of multiple halogen-doped all-inorganic perovskite quantum dots prepared in example 4 of the present invention (wherein the 1 st, 4 th and 8 th peaks respectively represent fluorescence emission spectra of all-inorganic perovskite quantum dots prepared in examples 1-3 and having single halogen doping, and the 2 nd and 3 rd peaks represent PbCl2、PbBr2Fluorescence emission spectra of the two halogen compound doped all-inorganic perovskite quantum dots, wherein the 5 th, 6 th and 7 th peaks are PbBr2、PbI2The fluorescence emission spectrum of the two halogen compound doped all-inorganic perovskite quantum dots is limited by the picture width, and a plurality of halogens are dopedOnly a selected part of the fluorescence emission spectrum of the hybrid all-inorganic perovskite quantum dot is reflected in fig. 3, the fluorescence emission spectrum of the all-inorganic perovskite quantum dot doped with various halogens in other proportions is close to the fluorescence emission spectrum of other quantum dots in fig. 3, and the spectrum ranges are different). As can be seen from FIG. 3, the fully inorganic perovskite quantum dots prepared by the two halogen composite doping methods have the same effect as single halogen doping methods, and both have good luminescence monochromaticity (the luminescence full width at half maximum is about 20nm) and high fluorescence quantum yield (more than 50%); the fluorescence spectra of the halogen-doped all-inorganic perovskite quantum dots with different proportions can be adjusted within 404nm-640 nm. Because the optimal spectral response wave bands of the photovoltaic devices based on different semiconductor materials are different, the invention can ensure that the prepared perovskite quantum dots are accurately matched with the photovoltaic devices with specific spectral response wave bands by controlling the doping proportion of a plurality of halogen ions, and further ensure that the solar fluorescent light collector based on the perovskite quantum dots can be applied to various photovoltaic devices based on different semiconductor materials.
Fig. 4 shows the variation of the reabsorption loss (a), the reemission loss (b), the photon escape loss (c) and the light collection efficiency (d) of the solar fluorescent light collector based on the all-inorganic perovskite quantum dots prepared in example 1 of the present invention with the doping concentration of the quantum dots. The doping concentration of the optimal all-inorganic perovskite quantum dot is 2.1 multiplied by 10-5At mol/L, about 73.9% of incident photons are not absorbed, the re-emission loss is 13.1%, the photon escape probability is 2.1%, and the average wavelength collection efficiency is 5.4%. Firstly, as the doping concentration of the quantum dots is gradually increased, the probability of non-absorption of photons in the fluorescent solar light collector is gradually reduced, which means that more incident photons are absorbed by the fluorescent solar light collector, and the corresponding average wavelength light collection efficiency is gradually increased. Subsequently, the doping concentration of the quantum dots is further increased, the number of absorbed photons in the fluorescent solar light collector is increased, the re-emission loss of the photons absorbed by the quantum dots is increased, the photon escape probability is slightly increased, and the light collection efficiency of the average wavelength of the fluorescent solar light collector reaches a peak value. Further increasing the doping concentration of the quantum dots, the light collecting efficiency of the average wavelength gradually decreases due to the increase of re-emission loss and photon escape probability. Thus, it is possible to provideThe optimal quantum dot doping concentration of the fluorescent solar light collecting device based on the all-inorganic perovskite quantum dots is 2.1 multiplied by 10-5mol/L, and the light collecting efficiency of the corresponding best solar fluorescence light collector is 5.4 percent.
The light collecting efficiency of the solar fluorescent light collectors prepared in the embodiments 2 and 3 of the invention is 5.3% and 5.2%, respectively.
The light collection efficiency of the solar fluorescent light collector prepared in the embodiment 4 of the invention is between 5.8 and 6.2 percent.
The light collecting efficiency of the solar fluorescent light collectors prepared in the embodiments 5 and 6 of the invention is 5.3% and 5.4%, respectively.
It should be noted that, because the light collecting efficiency of the solar fluorescence light collector has a huge relationship with the conditions such as the size, etc., the solar fluorescence light collector prepared in the above embodiments is smaller in size for easy detection, and if the solar fluorescence light collector is made into a larger size, the light collecting efficiency will be greatly improved, which can be at least more than 10%.
The collection efficiency in the present invention is a measure of the fluorescence solar collector, and is defined as the ratio of the number of collected photons to the number of incident photons at each wavelength, and the average wavelength collection efficiency is used as a measure herein, and is weighted and averaged according to the number of photons in the AM1.5 standard solar spectrum. Defined as the ratio of the number of photons collected by the solar cell to the number of photons incident on the collector. The light collection efficiency in the present invention was tested under AM1.5 standard solar spectrum conditions.
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.
Claims (10)
1. A preparation method of a solar fluorescence light collector based on all-inorganic perovskite quantum dots is characterized by comprising the following steps,
s1, preparing all-inorganic perovskite quantum dots: injecting the cesium-oleic acid mixed solution into lead halide precursor liquid by a thermal injection method to prepare halogen-doped all-inorganic perovskite quantum dots;
s2, preparation of the solar fluorescent light collector: dissolving all-inorganic perovskite quantum dots and a photoinitiator in an allyl monomer, mixing the allyl monomer with a thiol monomer to form a mixed solution, performing ultrasonic treatment on the mixed solution for 0.5-1.5min, pouring the mixed solution into a mold, performing drying treatment in a vacuum environment for 25-35min, heating at a constant temperature of 65-75 ℃ for 25-35min, irradiating by using an ultraviolet lamp for curing, demolding by curing, and performing cutting and polishing processes to obtain the all-inorganic perovskite quantum dot-based solar fluorescence collector.
2. The method according to claim 1, wherein the cesium-oleic acid mixed solution in the step S1 is prepared by mixing OA and Cs2CO3Adding into ODE, stirring and heating to 190-210 ℃ until the white powder is completely dissolved, and then preserving the heat for 0.8-1.2h at the temperature of 125-135 ℃ in a vacuum environment to prepare the cesium-oleic acid mixed solution.
3. The method according to claim 2, wherein the OA, Cs are used in the step S1 of preparing the cesium-oleic acid mixed solution2CO3The addition amount of ODE is calculated according to the following proportion: every 1g of Cs2CO3The mixture ratio is 2.6-3.4mLOA and 45-55mL ODE.
4. The method according to claim 1, wherein the lead halide precursor liquid in step S1 is prepared by: mixing OA, OLA, ODE and PbX2Mixing the solid powders, and treating at 90-110 deg.C for 25-35min in vacuum environment to obtain lead halide precursor liquid.
5. The method of claim 4, wherein the OA, OLA, ODE and PbX are used2The addition amount of the solid powder is calculated according to the following proportion: pb in an amount of 0.35 to 0.40mmol per unitX2The solid powder was prepared from 1ml OA, 1ml OLA and 10ml ODE.
6. The method according to claim 4, wherein PbX is added in step S12Is PbCl2、PbBr2、PbI2One or more of (a).
7. The method according to claim 4, wherein PbX is added in step S12Is PbCl2、PbBr2、PbI2Two or three of them.
8. The method as claimed in claim 5, wherein the thermal injection method in step S1 comprises heating the lead halide precursor solution to 135 ℃ in a vacuum environment, maintaining the temperature for 25-35min, heating to 165 ℃ at 155-.
9. The method according to claim 1 or 5, wherein the cesium-oleic acid solution is injected into the lead halide precursor liquid in the step S1 in a ratio of Cs to PbX2The molar ratio of (1) to (1-1.5).
10. The method according to claim 1, wherein the mixed solution of step S2 contains all-inorganic perovskite quantum dots at a concentration of 10-7-10-4mol/L。
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