CN114891496B - Environment-friendly copper-gallium-aluminum-sulfur zinc sulfide core-shell quantum dot and preparation method and application thereof - Google Patents
Environment-friendly copper-gallium-aluminum-sulfur zinc sulfide core-shell quantum dot and preparation method and application thereof Download PDFInfo
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- 239000002096 quantum dot Substances 0.000 title claims abstract description 85
- 239000011593 sulfur Substances 0.000 title claims abstract description 41
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 41
- 239000011258 core-shell material Substances 0.000 title claims abstract description 35
- 229910052984 zinc sulfide Inorganic materials 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000005083 Zinc sulfide Substances 0.000 title claims description 9
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 title claims description 9
- 239000002243 precursor Substances 0.000 claims abstract description 54
- 239000000243 solution Substances 0.000 claims abstract description 52
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000010438 heat treatment Methods 0.000 claims abstract description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 30
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000002347 injection Methods 0.000 claims abstract description 23
- 239000007924 injection Substances 0.000 claims abstract description 23
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 20
- 239000011701 zinc Substances 0.000 claims abstract description 20
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims abstract description 18
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 15
- CDZGJSREWGPJMG-UHFFFAOYSA-N copper gallium Chemical compound [Cu].[Ga] CDZGJSREWGPJMG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000007872 degassing Methods 0.000 claims abstract description 14
- -1 aluminum sulfur zinc sulfide Chemical group 0.000 claims abstract description 12
- 238000010926 purge Methods 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000010791 quenching Methods 0.000 claims abstract description 11
- 230000000171 quenching effect Effects 0.000 claims abstract description 11
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 239000010949 copper Substances 0.000 claims abstract description 7
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000006228 supernatant Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- DWRNSCDYNYYYHT-UHFFFAOYSA-K gallium(iii) iodide Chemical compound I[Ga](I)I DWRNSCDYNYYYHT-UHFFFAOYSA-K 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 5
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 3
- JTLBNHXAEWAFHT-UHFFFAOYSA-N aluminum zinc sulfide Chemical group [S-2].[Zn+2].[Al+3] JTLBNHXAEWAFHT-UHFFFAOYSA-N 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 238000005424 photoluminescence Methods 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 4
- 239000012792 core layer Substances 0.000 abstract 1
- 239000012295 chemical reaction liquid Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 238000006862 quantum yield reaction Methods 0.000 description 4
- SYBBXSBONIWLNR-UHFFFAOYSA-N [Zn+2].[S-2].[Al+3].[Cu+2] Chemical group [Zn+2].[S-2].[Al+3].[Cu+2] SYBBXSBONIWLNR-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000013082 photovoltaic technology Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052951 chalcopyrite Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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Abstract
The invention discloses an environment-friendly copper gallium aluminum sulfur zinc sulfide core-shell quantum dot and a preparation method and application thereof, and the method comprises the following steps: (1) Mixing gallium source, aluminum source, copper source and oleylamine, heating with nitrogen purge, injecting 1-dodecyl mercaptan, heating, degassing in inert gas environment, heating, injecting sulfur precursor solution, heating, quenching in water bath, centrifuging, and collecting to obtain CuGaAlS 2 Nuclear quantum dots; (2) CuGaAlS 2 After purifying the nuclear quantum dot, dissolving the nuclear quantum dot in 1-octadecene, then degassing at room temperature under nitrogen purging, then heating, then dropwise injecting zinc precursor solution, then dropwise injecting sulfur precursor solution, repeating the injection steps four times, heating, quenching in water bath, and centrifugally collecting to obtain the product. The quantum dot with the copper-gallium-aluminum-sulfur@zinc sulfide core-shell structure effectively passivates surface defects of a core layer, and improves photoluminescence yield and stability.
Description
Technical Field
The invention belongs to the technical field of quantum dot materials, and particularly relates to an environment-friendly copper gallium aluminum sulfur zinc sulfide core-shell quantum dot and a preparation method and application thereof.
Background
The solar fluorescent concentrator photovoltaic technology is a novel solar photoelectric conversion technology which directly utilizes solar energy and converts the solar energy into electric energy, and has a simple structure, and is generally composed of a transparent waveguide embedded with fluorescent materials and a solar cell loaded on the edge of the transparent waveguide. The fluorescent material can absorb short waves with higher energy in sunlight wave bands and then emit long waves, and the long waves can be transmitted to the solar cells at the edges of the waveguides through the total reflection effect, so that solar photoelectric conversion is realized. Compared with the traditional photovoltaic technology, the solar fluorescent condenser can generate electric energy, has the same transparent characteristic as glass, and is suitable for building integrated photovoltaic buildings. However, the current solar photoelectric conversion technology of the solar fluorescent concentrator based on the semiconductor colloid quantum dot cannot be put into practical application on a large scale, and the main limitation is that most quantum dots serving as fluorescent materials contain heavy metal elements such as lead, cadmium and the like.
Although colloidal semiconductor quantum dots have excellent optical properties including tunable absorption and emission spectra, high photoluminescence quantum yields, and excellent photostability. However, the current common quantum dots applied to high-performance solar fluorescent concentrators are mostly composed of highly toxic heavy metals which are fatal to human health and environment, and commercialization of the technology is hindered from the viewpoint of health and environmental protection. However, the performance of the solar fluorescent concentrator based on the environment-friendly quantum dot material is generally low, mainly because the quantum dots have multi-component characteristics and more surface defect states, the photoluminescence yield and stability are easy to reduce, and the most traditional and commonly used strategy for improving the solar fluorescent concentrator based on the environment-friendly quantum dot comprises adding a layer of material with larger band gap on the surface of the quantum dot for shell passivation, doping and the like.
The development of the environment-friendly core-shell quantum dots of the current I-III-VI ternary chalcopyrite system is mature, and the environment-friendly core-shell quantum dots comprise copper gallium zinc sulfide and copper aluminum zinc sulfide core-shell quantum dots. The copper-gallium-sulfur zinc sulfide quantum dot has direct band gap, high-efficiency luminous quantum yield, large Stokes shift and long-term stability, and is a common luminescent material. However, in the material preparation stage, due to the scarcity of gallium elements, high quality and expensive gallium precursors (expensive ultra-pure gallium iodide) are required for successful synthesis, which cannot meet the low cost-effectiveness requirements of industrial development. In contrast, copper aluminum zinc sulfide quantum dots are another attractive group I-III-VI core-shell quantum dot member, where the use of low cost and crust-rich aluminum precursors (inexpensive aluminum chloride) can largely meet the cost reduction needs of industrial development. However, the quantum yield of luminescence of copper aluminum zinc sulfide quantum dots is low, thus limiting the application of the quantum dots in luminescence.
Disclosure of Invention
Aiming at the prior art, the invention provides an environment-friendly copper gallium aluminum sulfur zinc sulfide core-shell quantum dot and a preparation method and application thereof, so as to solve the problems of high toxicity, low luminous yield and poor stability of the existing quantum dot.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: the preparation method of the environment-friendly copper gallium aluminum sulfur zinc sulfide core-shell quantum dot comprises the following steps:
(1) Synthesis of CuGaAlS 2 Nuclear quantum dots: mixing gallium source, aluminum source, copper source and oleylamine, heating to 65-75 ℃ with nitrogen purging, injecting 1-dodecyl mercaptan into the mixture, heating to 110-130 ℃, degassing in an inert gas environment for 55-65 min, heating to 170-190 ℃, injecting sulfur precursor solution into the mixture, maintaining for 4-6 min, heating to 210-230 ℃ and maintaining for 15-25 min, quenching in a water bath to stop reaction, and centrifuging to collect CuGaAlS 2 Nuclear quantum dots;
(2) Synthesizing core-shell quantum dot CuGaAlS 2 ZnS: cuGaAlS 2 After purifying the nuclear quantum dot, dissolving the nuclear quantum dot in 1-octadecene, then degassing at room temperature under nitrogen purging, then degassing at 110-130 ℃ for 25-35 min, then heating to 140-160 ℃, then dropwise injecting zinc precursor solution and keeping for 8-12 min, then dropwise injecting sulfur precursor solution and keeping for 8-12 min, repeating the injection steps four times, and then heatingAnd (3) keeping the temperature to 220-240 ℃ for 25-35 min, quenching in water bath, and centrifugally collecting.
The copper gallium aluminum sulfur zinc sulfide core-shell quantum dot can make up for the defects of the copper gallium aluminum sulfur zinc sulfide and copper aluminum sulfur zinc sulfide core-shell quantum dot, and has great potential in preparing high-performance and low-cost environment-friendly quantum dots and solar fluorescent concentrators thereof.
On the basis of the technical scheme, the invention can be improved as follows.
Further, the gallium source, the aluminum source and the copper source are gallium iodide, aluminum chloride and cuprous iodide respectively; in the step (1), the dosage ratio of the gallium source, the aluminum source, the copper source, the oleylamine, the 1-dodecyl mercaptan and the sulfur precursor solution is 0.25mmol to 0.5mmol to 4-6 ml to 0.4-0.6 ml to 0.5ml.
Further, the sulfur precursor solution of step (1) is prepared by the steps of: sulfur powder, oleylamine and 1-dodecyl mercaptan were ultrasonically mixed at a feed to liquid ratio of 1mmol to 0.75ml to 0.25 ml.
Further, cuGaAlS 2 The nuclear quantum dot purification process comprises the following steps: cuGaAlS 2 And mixing the nuclear quantum dots and toluene according to the volume ratio of 1:4, centrifuging at 3000 rpm, taking supernatant, adding ethanol, centrifuging at 12000 rpm, pouring out the supernatant, standing and airing to obtain the quantum dot.
Further, the sulfur precursor solution in step (2) is prepared by the steps of: carrying out ultrasonic mixing on sulfur powder, oleylamine and 1-dodecyl mercaptan according to a feed liquid ratio of 1mmol to 1.5ml to 0.5ml; the zinc precursor solution is prepared by the following steps: zinc stearate and 1-octadecene are ultrasonically mixed according to the feed liquid ratio of 1mmol to 5ml.
Further, the injection speed of the zinc precursor solution and the sulfur precursor solution in the step (2) is 0.2ml/min; cuGaAlS in step (2) 2 The dosage of the nuclear quantum dot, the 1-octadecene, the zinc precursor solution and the sulfur precursor solution is 1 ml:4-6 ml:4ml:1.6ml.
The invention also provides the environment-friendly copper gallium aluminum sulfur zinc sulfide core-shell quantum dot prepared by the preparation method.
The invention also provides application of the environment-friendly copper-gallium-aluminum-sulfur zinc sulfide core-shell quantum dot in preparation of a solar fluorescent condenser.
Further, the solar fluorescent concentrator consists of an organic polymeric transparent waveguide embedded with environment-friendly copper gallium aluminum zinc sulfide core-shell quantum dots serving as fluorescent materials and a solar cell loaded at the edge of the waveguide.
The beneficial effects of the invention are as follows:
the invention provides a preparation method of novel environment-friendly copper gallium aluminum sulfur zinc sulfide core-shell quantum dots, which is effectively applied to the photoelectric conversion technology of a solar fluorescent condenser and has good stability. This is mainly due to the effective passivation of CuGaAlS by ZnS shell 2 The (CGAS) core has a large number of surface defects, so that the stability is improved, the non-radiative recombination is effectively inhibited, and the photoluminescence quantum yield is improved, thereby improving the photoelectric conversion efficiency and the optical efficiency. Specifically, the single shell quantum dot does not have photoluminescence, so that the solar fluorescent concentrator cannot be prepared, and the saturated photocurrent of the solar fluorescent concentrator sensitized by the quantum dot with the core-shell structure reaches 5.6mA cm -2 The photoelectric conversion efficiency reaches 1.66%, and has good stability of 67% for two months.
Drawings
FIG. 1 is an electron microscope photograph of an environment-friendly copper gallium aluminum sulfur zinc sulfide core-shell quantum dot morphology;
FIG. 2 is a view of CuGaAlS under UV lamp irradiation 2 a/ZnS fluorescent solar concentrator (edge-emitting red);
FIG. 3 is a CuGaAlS-based 2 Photoelectric conversion performance test of solar fluorescent concentrator of ZnS core-shell quantum dot and two-month stability test.
Detailed Description
The following describes the present invention in detail with reference to examples.
Example 1
The preparation method of the environment-friendly copper-gallium-aluminum-sulfur zinc sulfide core-shell quantum dot comprises the following steps:
(1) Synthesis of CuGaAlS 2 (CGAS) core quantum dots: first, 0.25mmol of gallium iodide, 0.25mmol of aluminum chloride and 0.5mmol of aluminum chloride are addedPutting cuprous iodide and 5ml of oleylamine into a 50 ml three-neck flask with a magnetic stirrer, heating to 70 ℃, purging with nitrogen, injecting 0.5ml of 1-dodecyl mercaptan into the flask, heating to 120 ℃, degassing in a nitrogen environment for 60min, heating to 180 ℃, injecting 0.5ml of sulfur precursor solution into the flask at 180 ℃ and holding for 5min to form nuclear layer quantum dots, heating to 220 ℃ and holding for 20min, stopping reaction through water bath quenching, transferring into a centrifuge tube, centrifuging, collecting, and storing in a refrigerator at 4 ℃;
wherein the sulfur precursor solution is prepared by the steps of: under ultrasonic conditions, 1mmol of sulfur powder is dissolved in 0.75ml of oleylamine and 0.25ml of 1-dodecyl mercaptan;
(2) Synthesizing core-shell quantum dot CuGaAlS 2 ZnS: 1ml of CuGaAlS was taken 2 Dispersing the nuclear quantum dots in 4ml of toluene, centrifuging at 3000 rpm, taking supernatant, adding 7 ml of ethanol, centrifuging at 12000 rpm, pouring out the supernatant, standing and airing to obtain purified CGAS nuclear quantum dots; purifying CuGaAlS 2 Dissolving the nuclear quantum dot in 5ml of 1-octadecene, placing the solution into a 50 ml three-neck flask with a magnetic stirrer, degassing at room temperature under nitrogen purging, degassing at 120 ℃ for 30 minutes, heating to 150 ℃, then dropwise injecting 1ml of zinc precursor solution at an injection rate of 0.2ml/min by using an injection pump, injecting 0.4 ml of sulfur precursor solution at the same rate after ten minutes of injection, keeping for 10 minutes after injection, repeating the injection steps for four times, injecting 4ml of total zinc precursor solution, injecting 1.6ml of sulfur precursor solution, heating to 230 ℃ and keeping for 30 minutes after injection to grow ZnS shells, quenching the reaction by adopting a water bath method, transferring the reaction liquid into a centrifuge tube, centrifugally collecting the reaction liquid, and keeping the reaction liquid in a refrigerator at 4 ℃;
wherein the sulfur precursor solution is prepared by the steps of: under ultrasonic conditions, 1mmol of sulfur powder is dissolved in 1.5ml of oleylamine and 0.5ml of 1-dodecyl mercaptan;
wherein the zinc precursor solution is prepared by the steps of: under ultrasonic conditions, 1mmol of zinc stearate was dissolved in 5ml of 1-octadecene.
Example 2
The preparation method of the environment-friendly copper-gallium-aluminum-sulfur zinc sulfide core-shell quantum dot comprises the following steps:
(1) Synthesis of CuGaAlS 2 (CGAS) core quantum dots: firstly, putting 0.25 millimole of gallium iodide, 0.25 millimole of aluminum chloride, 0.5 millimole of cuprous iodide and 4 milliliters of oleylamine into a 50 milliliter three-necked flask with a magnetic stirrer, heating to 65 ℃ and purging with nitrogen, then injecting 0.4 milliliter of 1-dodecyl mercaptan into the three-necked flask, heating to 110 ℃, degassing in a nitrogen environment for 65 minutes, heating to 170 ℃, injecting 0.5 milliliter of sulfur precursor solution into the three-necked flask at 170 ℃ and maintaining the temperature for 6 minutes to form nuclear layer quantum dots, heating to 210 ℃ and maintaining the temperature for 25 minutes, stopping the reaction through water bath quenching, transferring into a centrifuge tube, centrifugally collecting the nuclear layer quantum dots, and storing the nuclear layer quantum dots in a refrigerator at 4 ℃;
wherein the sulfur precursor solution is prepared by the steps of: under ultrasonic conditions, 1mmol of sulfur powder is dissolved in 0.75ml of oleylamine and 0.25ml of 1-dodecyl mercaptan;
(2) Synthesizing core-shell quantum dot CuGaAlS 2 ZnS: 1ml of CuGaAlS was taken 2 Dispersing the nuclear quantum dots in 4ml of toluene, centrifuging at 3000 rpm, taking supernatant, adding 7 ml of ethanol, centrifuging at 12000 rpm, pouring out the supernatant, standing and airing to obtain purified CGAS nuclear quantum dots; purifying CuGaAlS 2 The nuclear quantum dots were dissolved in 4ml of 1-octadecene and put into a 50 ml three-necked flask with a magnetic stirrer, then degassed at room temperature under nitrogen purge, then degassed at 110 ℃ for 35 minutes, then warmed up to 140 ℃, then 1ml of zinc precursor solution was injected dropwise at an injection rate of 0.2ml/min using an injection pump, after 12 minutes of injection of zinc precursor solution, 0.4 ml of sulfur precursor solution was injected at the same rate and maintained for 12 minutes after injection, the above injection steps were repeated four times, the total of zinc precursor solution was injected 4ml, sulfur precursor solution was injected into 1.6ml, after the injection was completed, the temperature was warmed up to 220 ℃ and maintainedGrowing ZnS shells for 35 minutes, quenching the reaction by adopting a water bath method, transferring the reaction liquid into a centrifuge tube for centrifugal collection, and storing in a refrigerator at 4 ℃;
wherein the sulfur precursor solution is prepared by the steps of: under ultrasonic conditions, 1mmol of sulfur powder is dissolved in 1.5ml of oleylamine and 0.5ml of 1-dodecyl mercaptan;
wherein the zinc precursor solution is prepared by the steps of: under ultrasonic conditions, 1mmol of zinc stearate was dissolved in 5ml of 1-octadecene.
Example 3
The preparation method of the environment-friendly copper-gallium-aluminum-sulfur zinc sulfide core-shell quantum dot comprises the following steps:
(1) Synthesis of CuGaAlS 2 (CGAS) core quantum dots: firstly, putting 0.25 millimole of gallium iodide, 0.25 millimole of aluminum chloride, 0.5 millimole of cuprous iodide and 6 milliliters of oleylamine into a 50 milliliter three-necked flask with a magnetic stirrer, heating to 75 ℃, purging with nitrogen, injecting 0.6 milliliter of 1-dodecyl mercaptan into the three-necked flask, heating to 130 ℃, degassing in a nitrogen environment for 55 minutes, heating to 190 ℃, injecting 0.5 milliliter of sulfur precursor solution into the three-necked flask at 190 ℃, holding for 4 minutes to form nuclear layer quantum dots, heating to 230 ℃ and holding for 15 minutes, stopping the reaction through water bath quenching, transferring into a centrifuge tube, centrifugally collecting, and storing in a refrigerator at 4 ℃;
wherein the sulfur precursor solution is prepared by the steps of: under ultrasonic conditions, 1mmol of sulfur powder is dissolved in 0.75ml of oleylamine and 0.25ml of 1-dodecyl mercaptan;
(2) Synthesizing core-shell quantum dot CuGaAlS 2 ZnS: 1ml of CuGaAlS was taken 2 Dispersing the nuclear quantum dots in 4ml of toluene, centrifuging at 3000 rpm, taking supernatant, adding 7 ml of ethanol, centrifuging at 12000 rpm, pouring out the supernatant, standing and airing to obtain purified CGAS nuclear quantum dots; purifying CuGaAlS 2 The nuclear quantum dots were dissolved in 6ml of 1-octadecene and placed in a 50 ml three-necked flask with a magnetic stirrer, followed by degassing at room temperature under nitrogen purge, and further degassing at 130℃for 25 minutesAfter that, the temperature is raised to 160 ℃, 1ml of zinc precursor solution is injected dropwise at the injection rate of 0.2ml/min by using an injection pump, after 8 minutes of injection of zinc precursor solution, 0.4 ml of sulfur precursor solution is injected at the same rate, and after 8 minutes of injection, the injection steps are repeated four times, 4ml of total zinc precursor solution is injected, 1.6ml of sulfur precursor solution is injected, after the injection is completed, the temperature is raised to 240 ℃ and kept for 25 minutes to grow ZnS shells, finally, the reaction is quenched by adopting a water bath method, and the reaction liquid is transferred into a centrifuge tube to be centrifugally collected and stored in a refrigerator at 4 ℃;
wherein the sulfur precursor solution is prepared by the steps of: under ultrasonic conditions, 1mmol of sulfur powder is dissolved in 1.5ml of oleylamine and 0.5ml of 1-dodecyl mercaptan;
wherein the zinc precursor solution is prepared by the steps of: under ultrasonic conditions, 1mmol of zinc stearate was dissolved in 5ml of 1-octadecene.
Experimental example
CuGaAlS with core-shell structure of the invention 2 The ZnS quantum dots are used as fluorescent materials to prepare solar fluorescent concentrators with the size of 5cm x 0.15cm, and a photoelectric conversion test system of the solar fluorescent concentrators and solar cells is constructed to test the photoelectric conversion efficiency, the optical efficiency and the long-acting stability.
The solar fluorescent concentrator of the present invention was tested for performance using a standard am1.5g solar simulator as a light source, the results of which are shown in table 1:
table 1 solar fluorescent concentrator Performance test data
| Performance parameters | Photoelectric conversion efficiency | Optical efficiency | Two month stability |
| Example 1 | 1.66％ | 2.2％ | 67％ |
From the table, the novel environment-friendly core-shell quantum dot can construct a solar fluorescent concentrator with high performance and stability.
As can be seen from FIG. 1, the environment-friendly CuGaAlS of the present invention 2 The ZnS core-shell quantum dots are uniform in size distribution and have an average particle size of 6.2 nanometers.
As can be seen from fig. 3, the standard solar cell: v (V) oc :0.57V、J sc :30.57mA/cm 2 62.37 percent of FF and 10.87 percent of PCE. Solar fluorescent concentrator-standard solar cell: v (V) oc :0.45V、J sc :5.60mA/cm 2 65.84% of FF and 1.66% of PCE. After two months, solar fluorescent concentrator-standard solar cell: v (V) oc :0.44V、J sc :3.80mA/cm 2 、FF:60.06％、PCE:1.00％。
While specific embodiments of the invention have been described in detail in connection with the examples, it should not be construed as limiting the scope of protection of the patent. Various modifications and variations which may be made by those skilled in the art without the creative effort are within the scope of the patent described in the claims.
Claims (4)
1. The preparation method of the environment-friendly copper-gallium-aluminum-sulfur zinc sulfide core-shell quantum dot is characterized by comprising the following steps of:
(1) Synthesis of CuGaAlS 2 Nuclear quantum dots: mixing a gallium source, an aluminum source, a copper source and oleylamine, heating to 65-75 ℃ with nitrogen purging, injecting 1-dodecyl mercaptan into the mixture, and heating to 1Degassing at 10-130deg.C in inert gas environment for 55-65 min, heating to 170-190 deg.C, injecting sulfur precursor solution into the solution, holding for 4-6 min, heating to 210-230deg.C and holding for 15-25 min, quenching in water bath to stop reaction, centrifuging, and collecting to obtain CuGaAlS 2 Nuclear quantum dots;
(2) Synthesizing core-shell quantum dot CuGaAlS 2 ZnS: cuGaAlS 2 After purifying the nuclear quantum dot, dissolving the nuclear quantum dot in 1-octadecene, then degassing at room temperature under nitrogen purging, then degassing at 110-130 ℃ for 25-35 min, then heating to 140-160 ℃, then instilling zinc precursor solution dropwise and keeping for 8-12 min, injecting sulfur precursor solution dropwise, maintaining for 8-12 min, repeating the injection steps four times, heating to 220-240 ℃ and maintaining for 25-35 min, quenching in water bath, and centrifuging and collecting to obtain the sulfur precursor;
the gallium source, the aluminum source and the copper source are gallium iodide, aluminum chloride and cuprous iodide respectively; in the step (1), the dosage ratio of the gallium source, the aluminum source, the copper source, the oleylamine, the 1-dodecyl mercaptan and the sulfur precursor solution is 0.25mmol to 0.5mmol to 4-6 ml to 0.4-0.6 ml to 0.5ml;
the sulfur precursor solution of the step (1) is prepared by the following steps: carrying out ultrasonic mixing on sulfur powder, oleylamine and 1-dodecyl mercaptan according to a feed liquid ratio of 1mmol to 0.75ml to 0.25 ml;
the CuGaAlS 2 The nuclear quantum dot purification process comprises the following steps: cuGaAlS 2 Mixing the nuclear quantum dots and toluene according to a volume ratio of 1:4, centrifuging at 3000 rpm, taking supernatant, adding ethanol, centrifuging at 12000 rpm, pouring out the supernatant, standing and airing to obtain the quantum dot;
the sulfur precursor solution in step (2) is prepared by the following steps: carrying out ultrasonic mixing on sulfur powder, oleylamine and 1-dodecyl mercaptan according to a feed liquid ratio of 1mmol to 1.5ml to 0.5ml; the zinc precursor solution is prepared by the following steps: ultrasonically mixing zinc stearate and 1-octadecene according to a feed liquid ratio of 1mmol to 5ml;
the injection speed of the zinc precursor solution and the sulfur precursor solution in the step (2) is 0.2ml/min; cuGaAlS in step (2) 2 Nuclear quantum dot, 1-octadecene, zinc precursor solution and sulfur precursor solutionThe dosage of the liquid is 1 ml:4-6 ml:4ml:1.6ml.
2. The environment-friendly copper gallium aluminum sulfur zinc sulfide core-shell quantum dot prepared by the preparation method of claim 1.
3. The use of the environmentally friendly copper gallium aluminum sulfur zinc sulfide core-shell quantum dot according to claim 2 in the preparation of solar fluorescent concentrators.
4. A use according to claim 3, characterized in that: the solar fluorescent concentrator consists of an organic polymeric transparent waveguide embedded with environment-friendly copper gallium aluminum zinc sulfide core-shell quantum dots serving as fluorescent materials and a solar cell loaded at the edge of the waveguide.
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