CN108767123B - Perovskite solar cell based on co-doping of water-soluble and alcohol-soluble carbon quantum dots and preparation method thereof - Google Patents
Perovskite solar cell based on co-doping of water-soluble and alcohol-soluble carbon quantum dots and preparation method thereof Download PDFInfo
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Abstract
A perovskite solar cell based on co-doping of water-soluble and alcohol-soluble carbon quantum dots and a preparation method thereof belong to the technical field of perovskite solar cells. The composite material sequentially comprises an ITO conductive glass substrate, PEDOT doped with water-soluble carbon quantum dots, a PSS hole transport layer, a perovskite active layer, a PCBM electron transport layer doped with alcohol-soluble carbon quantum dots, a BCP hole blocking layer and an Ag anode. According to the invention, water-soluble carbon quantum dots are doped into a PEDOT-PSS hole transport layer, the coulomb acting force between the PEDOT and the PSS is reduced by utilizing the high conductivity and the surface activity of the carbon quantum dots, the conductivity of the PEDOT-PSS hole transport layer is improved, and the cell carrier transport is balanced. Meanwhile, alcohol-soluble carbon quantum dots are doped into the PCBM electron transport layer, and permeate into the polycrystalline perovskite gap by utilizing the smaller size of the PCBM electron transport layer, so that the crystal boundary defect of the perovskite layer is passivated, the carrier transport is improved, and the performance of the perovskite battery is further improved.
Description
Technical Field
The invention belongs to the technical field of perovskite solar cells, and particularly relates to a perovskite solar cell based on co-doping of water-soluble and alcohol-soluble carbon quantum dots and a preparation method thereof.
Background
The perovskite solar cell is widely researched by researchers around the world due to the advantages of low manufacturing cost, high efficiency and the like, wherein the inverse perovskite solar cell taking PEDOT, namely PSS as a hole transport layer and PCBM as an electron transport layer is widely applied due to the stable performance of the inverse perovskite solar cell, and although the conductive capability of the PEDOT is improved to a certain extent by adding the PSS, the film characteristics are influenced by the large coulomb acting force between the PEDOT and the PCBM, so that the electron transport performance of the device is limited. On the other hand, in the process of manufacturing the perovskite layer, the existence of crystal grain gaps among polycrystalline materials causes the light infiltration phenomenon caused by ion transmission, thereby hindering the charge transmission in the battery and influencing the performance improvement. The low-cost environment-friendly water-soluble and alcohol-soluble carbon quantum dot materials are respectively synthesized by a simple hydrothermal method and are respectively doped into water-soluble PEDOT (PSS) and alcohol-soluble PCBM, PSDOT is doped by utilizing the high conductivity and surface activity of the carbon quantum dots, PSS reduces the coulomb acting force between the PEDOT and the PSS, the conductivity of the carbon quantum dots is improved, and the current carrier transmission of the battery is balanced. Meanwhile, alcohol-soluble carbon quantum dots are doped into the PCBM electron transport layer, and permeate into the polycrystalline perovskite gap by utilizing the smaller size of the PCBM electron transport layer, so that the crystal boundary defect of the perovskite layer is passivated, the carrier transport is improved, and the performance of the perovskite battery is further improved.
Disclosure of Invention
The invention aims to provide a perovskite solar cell based on co-doping of water-soluble and alcohol-soluble carbon quantum dots and a preparation method thereof.
The invention relates to a perovskite solar cell based on co-doping of water-soluble and alcohol-soluble carbon quantum dots, which is formed by sequentially mixing an ITO conductive glass substrate/water-soluble carbon quantum dot-doped poly (3, 4-ethylenedioxythiophene): polystyrene sulfonic acid (PEDOT: PSS) hole transport layer/perovskite active layer/alcohol-soluble carbon quantum dot doped [6,6] -phenyl C61 methyl butyrate (PCBM) electron transport layer/Bathocuproine (BCP) hole blocking layer/Ag anode.
The invention synthesizes low-cost environment-friendly water-soluble and alcohol-soluble carbon quantum dot materials respectively by a simple hydrothermal method. Water-soluble carbon quantum dots are doped into a PEDOT (polymer stabilized organic light emitting diode) PSS (polymer stabilized sapphire substrate) hole transport layer, the coulomb acting force between the PEDOT and the PSS is reduced by utilizing the high conductivity and the surface activity of the carbon quantum dots, the conductivity of the PEDOT and the PSS is improved, and the cell carrier transport is balanced. Meanwhile, alcohol-soluble carbon quantum dots are doped into the PCBM electron transport layer, and permeate into the polycrystalline perovskite gap by utilizing the smaller size of the PCBM electron transport layer, so that the crystal boundary defect of the perovskite layer is passivated, the carrier transport is improved, and the performance of the perovskite battery is further improved. The thickness of the perovskite active layer is 250-350 nm, the thickness of the PEDOT-PSS hole transport layer is 20-30 nm, the thickness of the PCBM electron transport layer is 30-40 nm, and the thickness of the BCP hole blocking layer is 5-8 nm. The size of the carbon quantum dots is 5-9 nm, and the thickness of the Ag anode is 80-120 nm.
The invention relates to a preparation method of a perovskite solar cell based on co-doping of water-soluble and alcohol-soluble carbon quantum dots, which comprises the following steps: 1. synthesizing carbon quantum dots; 2. water-soluble carbon quantum dot doped PEDOT: preparing a PSS hole transport layer; 3. preparing a perovskite active layer; 4. preparing an alcohol-soluble carbon quantum dot doped PCBM electron transport layer; 5. preparing a BCP layer; 6. preparing Ag electrode and other steps. The method comprises the following specific steps:
1) and (3) synthesizing the carbon quantum dots.
a) Synthesis of water-soluble carbon quantum dots
Adding 0.5-1.5 g of citric acid and 0.5-1.5 g of thiourea (the mass ratio of the citric acid to the thiourea is 1: 0.95-1.05) into 5-15 mL of ultrapure water, ultrasonically stirring for 20-40 min to form a transparent clear solution, transferring the solution to a reaction kettle, reacting for 3-5 h under the hydrothermal condition of 140-180 ℃, and naturally cooling to room temperature; then adding the product into 25-35 mL of absolute ethyl alcohol, and centrifuging for 10-20 min at the rotating speed of 12000-16000 r/min; repeatedly adding the obtained precipitate into absolute ethyl alcohol, performing centrifugal operation for 1-2 times, transferring the product into a freeze dryer, and performing freeze drying at-80 to-50 ℃ for 45-50 hours to obtain water-soluble carbon quantum dots, wherein the size of the quantum dots is 5-9 nm;
b) synthesis of alcohol-soluble carbon quantum dots
Adding 0.5-1.5 g of citric acid and 0.5-1.5 g of urea (the mass ratio of the citric acid to the urea is 1: 0.95-1.05) into 8-15 mL of ultrapure water, carrying out ultrasonic stirring for 20-40 min to form a transparent clear solution, carrying out condensation reflux reaction at 150-170 ℃ for 5-8 h under the condition of oil bath, naturally cooling to room temperature, centrifuging for 13-17 min at the rotating speed of 10000-14000 r/min, adding the obtained precipitate into 25-35 mL of deionized water, and centrifuging for 13-17 min at the rotating speed of 10000-14000 r/min; repeatedly adding the obtained precipitate into deionized water, performing centrifugal operation for 1-2 times, transferring the product into a freeze dryer, performing freeze drying at-80 to-50 ℃ for 45-50 hours, adding the dried product into 25-35 mL of 1mg/mL polyvinylpyrrolidone (PVP) aqueous solution, stirring for 4-8 hours, performing rotary evaporation at 50-70 ℃, and performing vacuum drying on the product at 50-70 ℃ for 1-3 hours to obtain alcohol-soluble carbon quantum dots, wherein the size of the quantum dots is 5-9 nm;
2) treatment of substrates
Ultrasonically cleaning an ITO conductive glass substrate for 10-20 minutes by using a detergent, acetone, isopropanol and deionized water respectively, and drying by using nitrogen after cleaning;
3) preparation of hole transport layer
Adding 2-5 mg of water-soluble carbon quantum dots into 5-8 mL of PEDOT (PSS) solution (the doping ratio is 0.3-0.6 mg/mL), carrying out ultrasonic oscillation for 25-35 min under the ice-water bath condition, and then filtering by using a 0.22um filter head to obtain the PEDOT (PSS) solution doped with the water-soluble carbon quantum dots; spin-coating a water-soluble carbon quantum dot-doped PEDOT (PSS) solution for 40-60 s on the cleaned ITO conductive glass substrate at 3000-5000 rpm, and then annealing the ITO conductive glass substrate at 130-150 ℃ for 10-20 min, so that a water-soluble carbon quantum dot-doped PEDOT (PSS hole transport layer) with the thickness of 20-30 nm is prepared on the ITO conductive glass substrate;
4) preparation of perovskite active layer
a, preparation of active layer solution
Under the condition of room temperature, 450-500 mg of lead iodide (PdI)2) And 150-200 mg of Methyl Amine Iodide (MAI) (the molar ratio is 1: 1-1.4) dissolving in 0.5-1.5 mL of DMF, and stirring at a stirring speed of 400-600 rpm for 10-14 h to obtain a perovskite active layer solution;
b, preparation of active layer
Under the condition of 3000-5000 rpm, spinning a perovskite active layer solution on a water-soluble carbon quantum dot-doped PEDOT (Poly ethylene terephthalate) (PSS) hole transport layer for 25-35 s, and dripping 300-700 uL chlorobenzene serving as an anti-solvent on the spun perovskite active layer solution at the 5-8 s from the beginning of spinning to obtain a perovskite active layer with the thickness of 250-350 nm;
5) preparation of PCBM electron transport layer
Dissolving 15-25 mg of PCBM material in 0.5-1.5 mL of chlorobenzene at room temperature, and stirring at a stirring speed of 400-600 rpm for 1-3 hours; dissolving 0.5-1.5 mg of alcohol-soluble carbon quantum dots in the solution, and stirring for 9-12 hours to obtain an alcohol-soluble carbon quantum dot doped PCBM solution (the doping ratio is 0.5-2 mg/mL); then, spin-coating an alcohol-soluble carbon quantum dot-doped PCBM solution on the perovskite active layer for 40-60 seconds under the condition of 3000-5000 rpm to obtain an alcohol-soluble carbon quantum dot-doped PCBM electron transport layer with the thickness of 30-40 nm;
6) preparation of BCP layer hole blocking layer
At a pressure of 1X 10-3～1×10-5Under the condition of Pa, evaporating and plating BCP with the thickness of 5-8 nm on the PCBM electron transport layer doped with the alcohol-soluble carbon quantum dots, wherein the growth rate is
7) Ag electrode preparation
At a pressure of 1X 10-3～1×10-5Under the condition of Pa, an Ag (chemical reagent of national group Co., Ltd.) electrode is vapor-plated on the BCP layer, the thickness is 80-120 nm, and the growth speed isAnd then the perovskite solar cell based on the co-doping of the water-soluble and alcohol-soluble carbon quantum dots is prepared.
Drawings
FIG. 1: the invention discloses a structural schematic diagram of a perovskite solar cell based on co-doping of water-soluble and alcohol-soluble carbon quantum dots;
FIG. 2: the prepared perovskite solar cell (inversion structure) based on co-doping of water-soluble and alcohol-soluble carbon quantum dots and the traditional perovskite solar cell (inversion structure) without carbon dot modification have photocurrent curves.
As shown in figure 1, 1 is glass, 2 is an ITO conductive film, 3 is a water-soluble carbon quantum dot-doped PEDOT, namely a PSS hole transport layer, 4 is a perovskite active layer, 5 is an alcohol-soluble carbon quantum dot-doped PCBM layer, 6 is a BCP layer, and 7 is an Ag electrode.
As shown in FIG. 2, at 100mw/cm2The I-V characteristic curve is measured under the illumination of the solar simulator, the curve A is the traditional perovskite solar cell (the structure is ITO/PEDOT: PSS/perovskite/PCBM/BCP/Ag) without carbon point modification, and the curve B is the device of the invention. The results of FIG. 2 show that the short-circuit current, the fill factor and the energy conversion efficiency of the perovskite solar cell prepared by the invention are obviously improved by comparing the photocurrent curves of the perovskite solar cell with those of the traditional solar cell.
Detailed Description
1) And (3) synthesizing the carbon quantum dots.
a) Synthesis of water-soluble carbon quantum dots
Adding 1g of citric acid and 1g of thiourea into 10mL of ultrapure water, ultrasonically stirring for 30min to form a transparent clear solution, transferring the solution to a reaction kettle, reacting at 160 ℃ for 4h at high temperature and high pressure, naturally cooling to room temperature, adding the product into 30mL of absolute ethyl alcohol, centrifuging for 15min at the rotating speed of 15000r/min, adding the obtained precipitate into 30mL of absolute ethyl alcohol again, centrifuging for 15min at the rotating speed of 15000r/min, transferring the product into a freeze dryer, and freeze-drying for 48 h at-60 ℃ to obtain about 1g of water-soluble carbon quantum dots, wherein the size of the quantum dots is about 6 nm;
b) synthesis of alcohol-soluble carbon quantum dots
Adding 1g of citric acid and 1g of urea into 10mL of ultrapure water, ultrasonically stirring for 30min to form a transparent clear solution, condensing and refluxing for 6h at 160 ℃ under the condition of oil bath, naturally cooling to room temperature, centrifuging for 15min at the rotating speed of 12000r/min, adding the product into 30mL of deionized water, centrifuging for 15min at the rotating speed of 12000r/min, adding the obtained precipitate into 30mL of deionized water again, centrifuging for 15min at the rotating speed of 12000r/min, transferring the product into a freeze dryer, and freeze-drying for 48 h at the temperature of minus 60 ℃; then adding the obtained product into 30mL of PVP aqueous solution with the concentration of 1mg/mL, stirring for 6h, carrying out rotary evaporation on the reacted solution at the temperature of 60 ℃, and then drying the product in vacuum at the temperature of 60 ℃ for 2h to obtain about 0.9g of alcohol-soluble carbon quantum dots with the size of about 8 nm;
2) treatment of substrates
Ultrasonically cleaning an ITO conductive glass substrate for 15 minutes by using a detergent, acetone, isopropanol and deionized water respectively, and drying by using nitrogen after cleaning;
3) preparation of hole transport layer
Adding 3mg of water-soluble carbon quantum dots into 6mL of PEDOT (PSS) solution (the doping concentration of the water-soluble carbon quantum dots is 0.5mg/mL), carrying out ultrasonic oscillation for 30min in an ice-water bath, and then filtering by using a 0.22um filter head to obtain the PEDOT (PSS) solution doped with the water-soluble carbon quantum dots; putting the cleaned ITO into a spin coater, spin-coating a water-soluble carbon quantum dot-doped PEDOT, namely PSS solution for 50s at 4000rpm, and then annealing the ITO conductive glass substrate with the PEDOT, namely PSS sol at 140 ℃ for 15min to obtain a water-soluble carbon quantum dot-doped PEDOT, namely a PSS hole transport layer with the thickness of 25nm on the ITO conductive glass substrate;
4) preparation of perovskite active layer
a) Preparation of active layer solution
Under the condition of room temperature, the purchased commercial lead iodide PdI2462mg of material and 159mg of methyl amine iodide MAI (molar ratio is 1: 1) are dissolved in 1mL of DMF, and then stirred for 12h at the stirring speed of 500rpm, namely an active layer solution is prepared;
b) preparation of the active layer
Setting the rotation speed of a spin coater to 4000rpm, setting the time to 30s, spin-coating an active layer solution on a PEDOT (power off tin) PSS (patterned sapphire substrate) layer to prepare an active layer, and dropwise adding 500uL of chlorobenzene serving as an anti-solvent onto the spin-coated perovskite active layer solution at the 6 th from the beginning of rotation to prepare the active layer with the thickness of 300 nm;
5) preparation of PCBM electron transport layer
20mg of PCBM material was dissolved in 1mL chlorobenzene (Beijing carbofuran) at room temperature and then stirred at 500rpm for 2 h; dissolving 1mg of alcohol-soluble carbon quantum dots in the solution, and stirring for 10 hours to obtain an alcohol-soluble carbon quantum dot doped PCBM solution; setting the rotation speed of a spin coater to be 4000rpm, setting the time to be 45s, and spin-coating an alcohol-soluble carbon quantum dot-doped PCBM solution on the perovskite layer to prepare an alcohol-soluble carbon quantum dot-doped PCBM electron transport layer with the thickness of 35 nm;
6) preparation of BCP hole blocking layer
At a pressure of 1X 10-5Under the condition of Pa, 6nm of BCP is vapor-plated on the PCBM layer, and the growth rate is 0.1/s;
7) ag electrode preparation
At a pressure of 1X 10-5And (3) under the condition of Pa, an Ag (chemical reagent of national group Co., Ltd.) electrode is vapor-plated on the BCP layer, the thickness is 100nm, the growth speed is 3A/s, and the perovskite solar cell based on the co-doping of the water-soluble and alcohol-soluble carbon quantum dots is further prepared.
Claims (3)
1. A preparation method of a perovskite solar cell based on co-doping of water-soluble and alcohol-soluble carbon quantum dots comprises the following steps:
1) treatment of substrates
Ultrasonically cleaning an ITO conductive glass substrate for 10-20 minutes by using a detergent, acetone, isopropanol and deionized water respectively, and drying by using nitrogen after cleaning;
2) preparation of hole transport layer
Adding 2-5 mg of water-soluble carbon quantum dots into 5-8 mL of PEDOT (PSS), ultrasonically oscillating for 25-35 min under the condition of ice-water bath, and filtering by using a 0.22um filter head to obtain a water-soluble carbon quantum dot doped PEDOT (PSS); spin-coating a water-soluble carbon quantum dot-doped PEDOT (PSS) solution for 40-60 s on the cleaned ITO conductive glass substrate at 3000-5000 rpm, and then annealing the ITO conductive glass substrate at 130-150 ℃ for 10-20 min, so that a water-soluble carbon quantum dot-doped PEDOT (PSS hole transport layer) with the thickness of 20-30 nm is prepared on the ITO conductive glass substrate;
adding 0.5-1.5 g of citric acid and 0.5-1.5 g of thiourea into 5-15 mL of ultrapure water, ultrasonically stirring for 20-40 min to form a transparent clear solution, transferring the solution to a reaction kettle, reacting for 3-5 h under the hydrothermal condition of 140-180 ℃, and naturally cooling to room temperature; then adding the product into 25-35 mL of absolute ethyl alcohol, and centrifuging for 10-20 min at the rotating speed of 12000-16000 r/min; repeatedly adding the obtained precipitate into absolute ethyl alcohol, performing centrifugal operation for 1-2 times, transferring the product into a freeze dryer, and performing freeze drying at-80 to-50 ℃ for 45-50 hours to obtain water-soluble carbon quantum dots with the size of 5-9 nm;
3) preparation of perovskite active layer
Under the condition of 3000-5000 rpm, spinning a perovskite active layer solution on a water-soluble carbon quantum dot-doped PEDOT (Poly ethylene terephthalate) (PSS) hole transport layer for 25-35 s, and dripping 300-700 uL chlorobenzene serving as an anti-solvent on the spun perovskite active layer solution at the 5-8 s from the beginning of spinning to obtain a perovskite active layer with the thickness of 250-350 nm;
4) preparation of PCBM electron transport layer
Dissolving 15-25 mg of PCBM material in 0.5-1.5 mL of chlorobenzene at room temperature, and stirring at a stirring speed of 400-600 rpm for 1-3 hours; dissolving 0.5-1.5 mg of alcohol-soluble carbon quantum dots in the solution, and stirring for 9-12 hours to obtain an alcohol-soluble carbon quantum dot doped PCBM solution; then, spin-coating an alcohol-soluble carbon quantum dot-doped PCBM solution on the perovskite active layer for 40-60 seconds under the condition of 3000-5000 rpm to obtain an alcohol-soluble carbon quantum dot-doped PCBM electron transport layer with the thickness of 30-40 nm;
adding 0.5-1.5 g of citric acid and 0.5-1.5 g of urea into 8-15 mL of ultrapure water, ultrasonically stirring for 20-40 min to form a transparent clear solution, carrying out condensation reflux at 150-170 ℃ under an oil bath condition for 5-8 h, naturally cooling to room temperature, centrifuging for 13-17 min at the rotating speed of 10000-14000 r/min, adding the obtained precipitate into 25-35 mL of deionized water, and centrifuging for 13-17 min at the rotating speed of 10000-14000 r/min; repeatedly adding the obtained precipitate into deionized water, performing centrifugal operation for 1-2 times, transferring the product into a freeze dryer, performing freeze drying at-80 to-50 ℃ for 45-50 hours, adding the dried product into 25-35 mL of 1mg/mL polyvinylpyrrolidone aqueous solution, stirring for 4-8 hours, performing rotary evaporation at 50-70 ℃, and performing vacuum drying on the product at 50-70 ℃ for 1-3 hours to obtain alcohol-soluble carbon quantum dots with the size of 5-9 nm;
5) preparation of BCP layer hole blocking layer
At a pressure of 1X 10-3～1×10-5Under the condition of Pa, evaporating and plating BCP with the thickness of 5-8 nm on the PCBM electron transport layer doped with the alcohol-soluble carbon quantum dots, wherein the growth rate is
6) Ag electrode preparation
At a pressure of 1X 10-3～1×10-5Under the condition of Pa, an Ag electrode is vapor-plated on the BCP layer, the thickness is 80-120 nm, and the growth speed is
And then the perovskite solar cell based on the co-doping of the water-soluble and alcohol-soluble carbon quantum dots is prepared.
2. The preparation method of the perovskite solar cell based on co-doping of the water-soluble and alcohol-soluble carbon quantum dots, according to claim 1, is characterized in that: dissolving 450-500 mg of lead iodide and 150-200 mg of methyl amine iodide in 0.5-1.5 mL of DMF at room temperature, and stirring at a stirring speed of 400-600 rpm for 10-14 h to obtain a perovskite active layer solution.
3. A perovskite solar cell based on co-doping of water-soluble and alcohol-soluble carbon quantum dots is characterized in that: is prepared by the method of any one of claims 1 to 2.
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| CN115172055B (en) * | 2022-05-13 | 2023-05-12 | 湖南艾华集团股份有限公司 | Solid aluminum electrolytic capacitor based on doped PEDOT (proton exchange membrane) PSS (power system stabilizer) and preparation method thereof |
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| WO2016135484A1 (en) * | 2015-02-27 | 2016-09-01 | Perpetuus Research & Development Limited | A particle dispersion |
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