CN108878661B - Preparation method of carbon quantum dot modified perovskite solar cell - Google Patents

Preparation method of carbon quantum dot modified perovskite solar cell Download PDF

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CN108878661B
CN108878661B CN201810696864.XA CN201810696864A CN108878661B CN 108878661 B CN108878661 B CN 108878661B CN 201810696864 A CN201810696864 A CN 201810696864A CN 108878661 B CN108878661 B CN 108878661B
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quantum dot
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transport layer
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CN108878661A (en
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王洪强
郭鹏飞
杨小昆
叶谦
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Northwest University of Technology
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    • H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
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    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
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    • H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
    • H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
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    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
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    • H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
    • H10K30/152—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising zinc oxide, e.g. ZnO
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Abstract

the invention belongs to the technical field of solar cells, and relates to a preparation method of a carbon quantum dot modified perovskite solar cell. The preparation method comprises the following steps: irradiating the anti-solvent by using pulse laser to prepare a carbon quantum dot solution in situ; then spin-coating the perovskite precursor solution on a transparent conductive substrate covered with an electron transport layer, dripping the carbon quantum dot solution on the perovskite thin film in the spin-coating process, and forming the carbon quantum dot modified perovskite thin film after heat treatment; and finally, preparing a hole transport layer and a metal electrode to finish the preparation of the perovskite solar cell. The carbon quantum dots prepared by the method have controllable size and excellent dispersibility and stability, can be directly introduced into the perovskite thin film, and is beneficial to simplifying the perovskite preparation process. The carbon quantum dot modified perovskite solar cell prepared by the method has high photoelectric conversion efficiency, good stability and high practical application value, and the efficiency can reach more than 21% at most.

Description

Preparation method of carbon quantum dot modified perovskite solar cell
Technical Field
the invention belongs to the technical field of solar cells, and relates to a preparation method of a carbon quantum dot modified perovskite solar cell.
Background
in the photovoltaic field, the photoelectric conversion efficiency of the organic-inorganic hybrid perovskite solar cell prepared by a low-temperature solution method exceeds 20 percent, and the organic-inorganic hybrid perovskite solar cell can almost be comparable to a monocrystalline silicon solar cell. The most obvious advantage of the low-temperature preparation technology is that the preparation process of the battery can be simplified, and the quality of the film can be improved. However, the polycrystalline perovskite thin film prepared by the low-temperature solution method has a large number of defects on the surface and grain boundaries, and the defects can cause non-radiative recombination of carriers and accelerate the degradation of moisture and oxygen to the thin film, thereby reducing the performance of the battery. How to enhance the stability while improving the efficiency of the battery becomes a very critical issue.
The method for passivating perovskite surface interface defects by carrying organic small molecules or polymers through an anti-solvent is the most common method for modifying perovskite thin films at present. However, most small molecule compounds and polymers are poorly conductive and do not facilitate perovskite photogenerated carrier migration. The quantum dots, particularly the carbon quantum dots, are small in size, high in conductivity and high in mobility, are very suitable for modifying the surface and the grain boundary of the perovskite, and are beneficial to extraction and transmission of photon-generated carriers of the perovskite, so that the photoelectric conversion efficiency of the perovskite solar cell is improved. However, most of the carbon quantum dots are synthesized by a chemical method at present, and the process has some defects: such as long cycle, complicated process, high cost, uneven size, etc., and is difficult to be directly utilized in perovskite solar cells due to poor dispersibility. The preparation of carbon quantum dots based on cheap raw materials, controllable size and simplified process is found to be of great significance for developing high-efficiency and stable perovskite solar cells.
disclosure of Invention
The invention aims to provide a preparation method of a carbon quantum dot modified perovskite solar cell, so as to solve the problems in the background technology.
The invention adopts the technical scheme that a preparation method of a carbon quantum dot modified perovskite solar cell is specifically carried out according to the following steps:
s1, preparation of a carbon quantum dot solution: preparing a carbon quantum dot solution by irradiating an anti-solvent with pulsed laser in an anhydrous and oxygen-free environment;
S2, preparing the perovskite solar cell modified by the carbon quantum dots: and (2) spin-coating a perovskite precursor solution on the transparent conductive substrate covered with the electron transport layer, introducing the carbon quantum dot solution prepared in the step S1 onto the perovskite thin film in the spin-coating process, forming the perovskite thin film modified by the carbon quantum dots after heat treatment, then spin-coating a hole transport layer on the perovskite thin film modified by the carbon quantum dots, and finally thermally evaporating a metal electrode on the hole transport layer to prepare the perovskite solar cell modified by the carbon quantum dots.
Further, the antisolvent in S1 is a benzene solvent, and is one or more of toluene, ethylbenzene, o-xylene, p-xylene, m-xylene, chlorobenzene, o-dichlorobenzene, p-dichlorobenzene, m-dichlorobenzene, 1,2, 3-trichlorobenzene, 1,2, 4-trichlorobenzene, bromobenzene, and dibromobenzene, and is preferably chlorobenzene or toluene.
Further, the wavelength of the pulse laser in S1 is 266nm, 355nm, 532nm or 1064nm, the energy is 50-1000 mJ/pulse, the irradiation time is 1-60min, and the size of the prepared carbon quantum dot is 3-10 nm.
Further, perovskite precursors in S2 are AX and BX2A compound of the formula (I), wherein A is CH3NH3 +、HC(＝NH)NH2 +、Cs+、Rb+、K+B is Pb2 +，Sn2 +x is one or more of halogen ions, and the AX type compound precursor is preferably CH3NH3Br、HC(＝NH)NH3I. one or more of CsI, BX2The precursor of the type compound is preferably PbI2、BrI2one or more of (a).
Further, the transparent conductive substrate covered with the electron transport layer is obtained by spin-coating the electron transport layer on the transparent conductive substrate, in S2, a perovskite precursor solution is spin-coated on the transparent conductive substrate covered with the electron transport layer, two steps of spin-coating are performed at a low speed of 2000rpm/10S and a high speed of 4000rpm/30S, the carbon quantum dot solution prepared in S1 is dropwise added when the remaining 5-10S are spin-coated, the carbon quantum dot modified perovskite thin film is prepared after heat treatment at 100 ℃ for 10-90min, the ratio of the usage amount of the perovskite precursor solution to the carbon quantum dot solution is 0.1-1mg/mL, and the thickness of the thin film is 300-700 nm.
Further, the transparent conductive matrix in S2 is one of fluorine-doped tin dioxide, indium tin oxide, and a flexible matrix.
further, in S2, the electron transport layer is made of one or more of titanium dioxide, tin dioxide, zinc oxide, and [6,6] -phenyl carbon 6-methyl butyrate, preferably titanium dioxide, and the thickness of the electron transport layer is 30-100 nm.
Further, the material of the hole transport layer in S2 is 2,2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9 '-spirobifluorene, poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine ], poly (3-hexylthiophene-2, 5-diyl), polyethylenedioxythiophene-poly (styrenesulfonate), one of cuprous thiocyanate, preferably 2,2',7,7 '-tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene (Spiro-ome tad), and the thickness of the hole transport layer is 100 to 200 nm.
Further, the metal electrode in S2 is one of gold, silver and aluminum, and the thickness of the metal electrode is 60 to 120nm, preferably 80 nm.
The invention has the beneficial effects that: (1) the pulse laser irradiation anti-solvent method can directly prepare carbon quantum dots with controllable concentration and size, high dispersibility and stability, can be directly put into use without complex processes such as hydrothermal, ligand exchange, centrifugal drying and the like, and has good dispersibility and high stability compared with the carbon quantum dots prepared by the traditional preparation method; (2) the method can directly introduce the carbon quantum dot solution into the perovskite thin film spin coating preparation process, can prepare the perovskite thin film with carbon quantum passivation without independently preparing the carbon quantum dot-anti-solvent solution, and has the advantages of simple process, convenient operation and obvious effect compared with the existing preparation method of carbon quantum dot modified perovskite; (3) the perovskite thin-film solar cell modified by the carbon quantum dots has high efficiency and good stability, the photoelectric conversion efficiency is increased to more than 21% from 15% of the basic efficiency, the photoelectric conversion efficiency and the stability of the perovskite thin-film solar cell prepared by the low-temperature solution method are greatly improved, and the perovskite thin-film solar cell has extremely high application prospect.
drawings
FIG. 1 is a schematic structural diagram of a carbon quantum dot modified perovskite solar cell according to the present invention;
FIG. 2 is a transmission electron micrograph of carbon quantum dots prepared in example 1;
FIG. 3 is a current-voltage plot of carbon quantum dot modified and unmodified perovskite solar cells prepared in example 1;
FIG. 4 is a transmission electron micrograph of carbon quantum dots prepared in example 2;
Fig. 5 is a current-voltage plot of the carbon quantum dot modified perovskite solar cell prepared in example 2;
FIG. 6 is a transmission electron micrograph of carbon quantum dots prepared in example 3;
Fig. 7 is a current-voltage plot of the carbon quantum dot modified perovskite solar cell prepared in example 3;
FIG. 8 is a transmission electron micrograph of carbon quantum dots prepared in example 4;
Fig. 9 is a current-voltage plot of the carbon quantum dot modified perovskite solar cell prepared in example 4;
FIG. 10 is a transmission electron micrograph of carbon quantum dots prepared in example 5;
fig. 11 is a current-voltage plot of the carbon quantum dot modified perovskite solar cell prepared in example 5;
FIG. 12 is a transmission electron micrograph of carbon quantum dots prepared in example 6;
Fig. 13 is a current-voltage plot of the carbon quantum dot modified perovskite solar cell prepared in example 6.
Description of reference numerals:
1. A transparent conductive substrate; 2. an electron transport layer; 3. a perovskite-carbon quantum dot composite layer; 4. carbon quantum dots; 5. a hole transport layer; 6. and a metal electrode.
Detailed Description
The technical solutions of the present invention are further described below with reference to specific examples, but it should be understood that the scope of the present invention is not limited by the specific examples. The applicant states that the above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited by the above examples, and any other equivalent replacement modes of laser energy, wavelength change, anti-solvent substitution, combination, perovskite composition change, and carbon quantum dot introduction amount and time without departing from the spirit and principle of the present invention are included in the protection scope of the present invention.
Example 1
A preparation method of a carbon quantum dot modified perovskite solar cell is specifically carried out according to the following steps:
s1, irradiating 6mL of chlorobenzene antisolvent by using pulse laser with the wavelength of 355nm and the energy of 100mJ for 10min under the anhydrous and anaerobic conditions to prepare carbon quantum dots with the size of about 3nm and the concentration of 0.1mg/mL, as shown in a transmission electron microscope photo of a picture 2;
s2, selecting FTO glass (fluorine-doped SnO) with sheet resistance of 15 omega/sq, thickness of 2.2mm and transmittance of 84.5%2transparent conductive glass) is used as a conductive substrate, FTO glass is sequentially subjected to ultrasonic cleaning in a glass cleaning agent, acetone and absolute ethyl alcohol for 20min, then is dried by blowing with nitrogen, and the dried glass is cleaned in an ozone plasma cleaning machine for 15min to remove organic matters on the surface of the glass and enhance the hydrophilicity of the surface;
s3, selecting TiO2As an electron transport layer of a perovskite solar cell: mixing 100 mu L of bis (acetylacetone) diisopropyl titanate with 1mL of isopropanol, stirring for 2h, filtering the stirred mixed solution for later use, and taking 50 mu L of prepared TiO2dripping the precursor on FTO glass with surface treatment, spin-coating at 2000r/min for 60s, placing the spin-coated glass on a heating table, heat-treating at 150 deg.C for 10min, placing in a box furnace, and holding at 500 deg.C for 60min to obtain dense TiO with thickness of 50nm2A layer;
S4, preparing 1.2mol/L Cs in an argon glove box0.05FA0.81MA0.14PbI2.55Br0.45Perovskite precursor: take 15.6mg CH3NH3I，166.6mg HC(＝NH)NH3I，19.1mg CH3NH3Br，474.4mg PbI2and 62.8mg of PbBr2Mixing and adding 800 mu L of dimethylformamide and 200 mu L of dimethyl sulfoxide into a small reagent bottle, stirring the mixed solution for 2h at 60 ℃, and filtering by using an organic filter head to obtain 1mL of 1.2mol/L perovskite precursor solution for experiment;
s5, dripping 25 mul of the perovskite precursor solution to 15 x 15mm2Coated with an electron transport layer of TiO2The FTO substrate is coated with 10S of low-speed (2000rmp) spin coating and 30S of high-speed (4000rmp) spin coating, 200 mul of the carbon quantum dot solution prepared in the step S1 is dripped in three seconds when the 10S are remained, and the FTO substrate is thermally treated for 1h at 100 ℃ to prepare the carbon quantum dot solution with a uniform and flat surface and a thickness of 600nmCarbon quantum dot-modified perovskite thin films;
s6, spinning and coating a hole transport layer Spiro-OMeTAD on the carbon quantum dot modified perovskite film, wherein the thickness is 150nm, and oxidizing in air for 12 h;
S7, evaporating a layer with the area of 0.1cm2And an Au electrode with the thickness of 80nm to obtain the carbon quantum dot modified perovskite solar cell, wherein the structural schematic diagram of the perovskite solar cell is shown in figure 1.
The highest photoelectric conversion efficiency of the cell was measured to be 18.79%, and the highest efficiency of the cell without the carbon quantum dots was measured to be 17.45%, as shown in fig. 3.
Example 2
A preparation method of a carbon quantum dot modified perovskite solar cell is characterized by comprising the following steps:
s1, irradiating 6mL of chlorobenzene antisolvent by using pulse laser with the wavelength of 355nm and the energy of 100mJ for 30min under the anhydrous and anaerobic conditions to prepare a carbon quantum dot with the size of about 3nm and the concentration of 0.6mg/mL, wherein as shown in a transmission electron microscope photo of a picture in figure 4, compared with the example 1, the carbon quantum dot has the unchanged size and the increased concentration;
S2, selecting FTO glass with sheet resistance of 15 omega/sq, thickness of 2.2mm and transmittance of 84.5% as a conductive substrate, ultrasonically cleaning the FTO glass in a glass cleaning agent, acetone and absolute ethyl alcohol for 20min in sequence, blow-drying the FTO glass by nitrogen, cleaning the blow-dried glass in an ozone plasma cleaning machine for 15min, removing organic matters on the surface of the glass and enhancing the hydrophilicity of the surface;
S3, selecting TiO2As an electron transport layer of a perovskite solar cell: mixing 100 mu L of bis (acetylacetone) diisopropyl titanate with 1mL of isopropanol, stirring for 2h, filtering the stirred mixed solution for later use, and taking 50 mu L of prepared TiO2Dripping the precursor on FTO glass with surface treatment, spin-coating at 2000r/min for 60s, placing the spin-coated glass on a heating table, heat-treating at 150 deg.C for 10min, placing in a box furnace, and holding at 500 deg.C for 60min to obtain dense TiO with thickness of 50nm2A layer;
S4, preparing 1.2mol/L Cs in an argon glove box0.05FA0.81MA0.14PbI2.55Br0.45Perovskite precursor: take 15.6mg CH3NH3I，166.6mg HC(＝NH)NH3I，19.1mg CH3NH3Br，474.4mg PbI2And 62.8mg of PbBr2Mixing and adding 800 mu L of dimethylformamide and 200 mu L of dimethyl sulfoxide into a small reagent bottle, stirring the mixed solution for 2h at 60 ℃, and filtering by using an organic filter head to obtain 1mL of 1.2mol/L perovskite precursor solution for experiment;
s5, dripping 25 mul of the perovskite precursor to 15 x 15mm2coated with an electron transport layer of TiO2On the FTO substrate, performing low-speed (2000rmp) spin coating for 10S, performing high-speed (4000rmp) spin coating for 30S, dripping 200 mu l of the carbon quantum dot solution prepared in the step S1 within three seconds when the 10S are remained, and performing heat treatment at 100 ℃ for 1h to prepare the carbon quantum dot modified perovskite thin film with a uniform and flat surface and a thickness of 600 nm;
S6, spinning and coating a hole transport layer Spiro-OMeTAD on the carbon quantum dot modified perovskite film, wherein the thickness is 150nm, and oxidizing in air for 12 h;
S7, evaporating a layer with the area of 0.1cm2And an Au electrode with the thickness of 80nm to obtain the carbon quantum dot modified perovskite solar cell.
the highest photoelectric conversion efficiency of the cell was measured to be 19.74%, as shown in fig. 5.
Example 3
A preparation method of a carbon quantum dot modified perovskite solar cell is characterized by comprising the following steps:
S1, irradiating 6mL of chlorobenzene antisolvent by using pulse laser with the wavelength of 355nm and the energy of 200mJ for 30min under the anhydrous and anaerobic conditions to prepare a carbon quantum dot with the size of about 5nm and the concentration of 0.6mg/mL, wherein as shown in a transmission electron microscope photo of a picture in figure 6, compared with the example 2, the carbon quantum dot is increased in size and unchanged in concentration;
S2, selecting FTO glass with sheet resistance of 15 omega/sq, thickness of 2.2mm and transmittance of 84.5% as a conductive substrate, ultrasonically cleaning the FTO glass in a glass cleaning agent, acetone and absolute ethyl alcohol for 20min in sequence, blow-drying the FTO glass by nitrogen, cleaning the blow-dried glass in an ozone plasma cleaning machine for 15min, removing organic matters on the surface of the glass and enhancing the hydrophilicity of the surface;
S3, selecting TiO2As an electron transport layer of a perovskite solar cell: mixing 100 mu L of bis (acetylacetone) diisopropyl titanate with 1mL of isopropanol, stirring for 2h, filtering the stirred mixed solution for later use, and taking 50 mu L of prepared TiO2dripping the precursor on FTO glass with surface treatment, spin-coating at 2000r/min for 60s, placing the spin-coated glass on a heating table, heat-treating at 150 deg.C for 10min, placing in a box furnace, and holding at 500 deg.C for 60min to obtain dense TiO with thickness of 50nm2A layer;
S4, preparing 1.2mol/L Cs in an argon glove box0.05FA0.81MA0.14PbI2.55Br0.45Perovskite precursor: take 15.6mg CH3NH3I，166.6mg HC(＝NH)NH3I，19.1mg CH3NH3Br，474.4mg PbI2And 62.8mg of PbBr2Mixing and adding 800 mu L of dimethylformamide and 200 mu L of dimethyl sulfoxide into a small reagent bottle, stirring the mixed solution for 2h at 60 ℃, and filtering by using an organic filter head to obtain 1mL of 1.2mol/L perovskite precursor solution for experiment;
S5, dripping 25 mul of the perovskite precursor to 15 x 15mm2coated with an electron transport layer of TiO2On the FTO substrate, performing low-speed (2000rmp) spin coating for 10S, performing high-speed (4000rmp) spin coating for 30S, dripping 200 mu l of the carbon quantum dot solution prepared in the step S1 within three seconds when the 10S are remained, and performing heat treatment at 100 ℃ for 1h to prepare the carbon quantum dot modified perovskite thin film with a uniform and flat surface and a thickness of 600 nm;
S6, spinning and coating a hole transport layer Spiro-OMeTAD on the carbon quantum dot modified perovskite film, wherein the thickness is 150nm, and oxidizing in air for 12 h;
S7, evaporating a layer with the area of 0.1cm2And an Au electrode with the thickness of 80nm to obtain the perovskite modified by the carbon quantum dotsa solar cell.
the highest photoelectric conversion efficiency of the cell was measured to be 21.09%, as shown in fig. 7.
Example 4
A preparation method of a carbon quantum dot modified perovskite solar cell is characterized by comprising the following steps:
S1, irradiating 6mL of chlorobenzene antisolvent by using pulse laser with the wavelength of 355nm and the energy of 400mJ for 30min under the anhydrous and anaerobic conditions to prepare a carbon quantum dot with the size of about 10nm and the concentration of 0.6mg/mL, wherein as shown in a transmission electron microscope photo of a picture in figure 8, compared with the example 3, the carbon quantum dot is increased in size and unchanged in concentration;
S2, selecting FTO glass with sheet resistance of 15 omega/sq, thickness of 2.2mm and transmittance of 84.5% as a conductive substrate, ultrasonically cleaning the FTO glass in a glass cleaning agent, acetone and absolute ethyl alcohol for 20min in sequence, blow-drying the FTO glass by nitrogen, cleaning the blow-dried glass in an ozone plasma cleaning machine for 15min, removing organic matters on the surface of the glass and enhancing the hydrophilicity of the surface;
s3, selecting TiO2As an electron transport layer of a perovskite solar cell: mixing 100 mu L of bis (acetylacetone) diisopropyl titanate with 1mL of isopropanol, stirring for 2h, filtering the stirred mixed solution for later use, and taking 50 mu L of prepared TiO2dripping the precursor on FTO glass with surface treatment, spin-coating at 2000r/min for 60s, placing the spin-coated glass on a heating table, heat-treating at 150 deg.C for 10min, placing in a box furnace, and holding at 500 deg.C for 60min to obtain dense TiO with thickness of 50nm2a layer;
S4, preparing 1.2mol/L Cs in an argon glove box0.05FA0.81MA0.14PbI2.55Br0.45Perovskite precursor: take 15.6mg CH3NH3I，166.6mg HC(＝NH)NH3I，19.1mg CH3NH3Br，474.4mg PbI2And 62.8mg of PbBr2mixing and adding 800 μ L of dimethylformamide and 200 μ L of dimethyl sulfoxide into a small reagent bottle, stirring the mixed solution at 60 deg.C for 2h, and organically filteringfiltering to obtain 1mL of 1.2mol/L perovskite precursor solution for experiment;
S5, dripping 25 mul of the perovskite precursor to 15 x 15mm2Coated with an electron transport layer of TiO2On the FTO substrate, performing low-speed (2000rmp) spin coating for 10S, performing high-speed (4000rmp) spin coating for 30S, dripping 200 mu l of the carbon quantum dot solution prepared in the step S1 within three seconds when the 10S are remained, and performing heat treatment at 100 ℃ for 1h to prepare the carbon quantum dot modified perovskite thin film with a uniform and flat surface and a thickness of 600 nm;
s6, spinning and coating a hole transport layer Spiro-OMeTAD on the carbon quantum dot modified perovskite film, wherein the thickness is 150nm, and oxidizing in air for 12 h;
S7, evaporating a layer with the area of 0.1cm2and an Au electrode with the thickness of 80nm to obtain the carbon quantum dot modified perovskite solar cell.
The highest photoelectric conversion efficiency of the cell was measured to be 18.28%, as shown in fig. 9.
Example 5
A preparation method of a carbon quantum dot modified perovskite solar cell is characterized by comprising the following steps:
S1, irradiating 6mL of chlorobenzene antisolvent by using pulse laser with the wavelength of 532nm and the energy of 200mJ for 30min under the anhydrous and oxygen-free conditions to prepare a carbon quantum dot with the size of about 5nm and the concentration of 0.8mg/mL, wherein as shown in a transmission electron micrograph of FIG. 10, the carbon quantum dot has the unchanged size and the increased concentration compared with the embodiment 3;
S2, selecting FTO glass with sheet resistance of 15 omega/sq, thickness of 2.2mm and transmittance of 84.5% as a conductive substrate, ultrasonically cleaning the FTO glass in a glass cleaning agent, acetone and absolute ethyl alcohol for 20min in sequence, blow-drying the FTO glass by nitrogen, cleaning the blow-dried glass in an ozone plasma cleaning machine for 15min, removing organic matters on the surface of the glass and enhancing the hydrophilicity of the surface;
s3, selecting TiO2as an electron transport layer of a perovskite solar cell: mixing 100 mu L of bis (acetylacetone) diisopropyl titanate with 1mL of isopropanol, stirring for 2h, and filtering the stirred mixed solution for later useTaking 50 mu L of prepared TiO2Dripping the precursor on FTO glass with surface treatment, spin-coating at 2000r/min for 60s, placing the spin-coated glass on a heating table, heat-treating at 150 deg.C for 10min, placing in a box furnace, and holding at 500 deg.C for 60min to obtain dense TiO with thickness of 50nm2A layer;
S4, preparing 1.2mol/L Cs in an argon glove box0.05FA0.81MA0.14PbI2.55Br0.45perovskite precursor: take 15.6mg CH3NH3I，166.6mg HC(＝NH)NH3I，19.1mg CH3NH3Br，474.4mg PbI2and 62.8mg of PbBr2mixing and adding 800 mu L of dimethylformamide and 200 mu L of dimethyl sulfoxide into a small reagent bottle, stirring the mixed solution for 2h at 60 ℃, and filtering by using an organic filter head to obtain 1mL of 1.2mol/L perovskite precursor solution for experiment;
S5, dripping 25 mul of the perovskite precursor to 15 x 15mm2Coated with an electron transport layer of TiO2on the FTO substrate, performing low-speed (2000rmp) spin coating for 10S, performing high-speed (4000rmp) spin coating for 30S, dripping 200 mu l of the carbon quantum dot solution prepared in the step S1 within three seconds when the 10S are remained, and performing heat treatment at 100 ℃ for 1h to prepare the carbon quantum dot modified perovskite thin film with a uniform and flat surface and a thickness of 600 nm;
s6, spinning and coating a hole transport layer Spiro-OMeTAD on the carbon quantum dot modified perovskite film, wherein the thickness is 150nm, and oxidizing in air for 12 h;
S7, evaporating a layer with the area of 0.1cm2and an Au electrode with the thickness of 80nm to obtain the carbon quantum dot modified perovskite solar cell.
The highest photoelectric conversion efficiency of the cell was measured to be 19.82%, as shown in fig. 11.
Example 6
A preparation method of a carbon quantum dot modified perovskite solar cell is characterized by comprising the following steps:
S1, irradiating 6mL of chlorobenzene antisolvent by using pulse laser with the wavelength of 1064nm and the energy of 200mJ for 30min under the anhydrous and anaerobic conditions to prepare a carbon quantum dot with the size of about 5nm and the concentration of 1mg/mL, wherein as shown in a transmission electron micrograph of a picture in FIG. 12, compared with the example 3, the carbon quantum dot has the increased size and the increased concentration;
S2, selecting FTO glass with sheet resistance of 15 omega/sq, thickness of 2.2mm and transmittance of 84.5% as a conductive substrate, ultrasonically cleaning the FTO glass in a glass cleaning agent, acetone and absolute ethyl alcohol for 20min in sequence, blow-drying the FTO glass by nitrogen, cleaning the blow-dried glass in an ozone plasma cleaning machine for 15min, removing organic matters on the surface of the glass and enhancing the hydrophilicity of the surface;
S3, selecting TiO2As an electron transport layer of a perovskite solar cell: mixing 100 mu L of bis (acetylacetone) diisopropyl titanate with 1mL of isopropanol, stirring for 2h, filtering the stirred mixed solution for later use, and taking 50 mu L of prepared TiO2Dripping the precursor on FTO glass with surface treatment, spin-coating at 2000r/min for 60s, placing the spin-coated glass on a heating table, heat-treating at 150 deg.C for 10min, placing in a box furnace, and holding at 500 deg.C for 60min to obtain dense TiO with thickness of 50nm2a layer;
s4, preparing 1.2mol/L Cs in an argon glove box0.05FA0.81MA0.14PbI2.55Br0.45Perovskite precursor: take 15.6mg CH3NH3I，166.6mg HC(＝NH)NH3I，19.1mg CH3NH3Br，474.4mg PbI2and 62.8mg of PbBr2Mixing and adding 800 mu L of dimethylformamide and 200 mu L of dimethyl sulfoxide into a small reagent bottle, stirring the mixed solution for 2h at 60 ℃, and filtering by using an organic filter head to obtain 1mL of 1.2mol/L perovskite precursor solution for experiment;
s5, dripping 25 mul of the perovskite precursor to 15 x 15mm2Coated with an electron transport layer of TiO2on the FTO substrate, performing low-speed (2000rmp) spin coating for 10S, performing high-speed (4000rmp) spin coating for 30S, dripping 200 mu l of the carbon quantum dot solution prepared in the step S1 within three seconds when the 10S are remained, and performing heat treatment at 100 ℃ for 1h to prepare the carbon quantum dot modified perovskite thin film with a uniform and flat surface and a thickness of 600 nm;
S6, spinning and coating a hole transport layer Spiro-OMeTAD on the carbon quantum dot modified perovskite film, wherein the thickness is 150nm, and oxidizing in air for 12 h;
S7, evaporating a layer with the area of 0.1cm2and an Au electrode with the thickness of 80nm to obtain the carbon quantum dot modified perovskite solar cell.
the highest photoelectric conversion efficiency of the cell was measured to be 17.1%, as shown in fig. 13.
The above disclosure is only for the specific embodiment of the present invention, but the embodiment of the present invention is not limited thereto, and any variations that can be made by those skilled in the art should fall within the scope of the present invention.

Claims (9)

1. A preparation method of a carbon quantum dot modified perovskite solar cell is characterized by comprising the following steps:
S1, preparation of a carbon quantum dot solution: preparing a carbon quantum dot solution by irradiating an anti-solvent with pulsed laser in an anhydrous and oxygen-free environment; the anti-solvent is a benzene solvent;
S2, preparing the perovskite solar cell modified by the carbon quantum dots: and (2) spin-coating a perovskite precursor solution on the transparent conductive substrate covered with the electron transport layer, introducing the carbon quantum dot solution prepared in the step S1 onto the perovskite thin film in the spin-coating process, forming the perovskite thin film modified by the carbon quantum dots after heat treatment, then spin-coating a hole transport layer on the perovskite thin film modified by the carbon quantum dots, and finally thermally evaporating a metal electrode on the hole transport layer to prepare the perovskite solar cell modified by the carbon quantum dots.
2. The method for preparing the carbon quantum dot modified perovskite solar cell as claimed in claim 1, wherein the anti-solvent in S1 is a benzene solvent and is one or more of toluene, ethylbenzene, o-xylene, p-xylene, m-xylene, chlorobenzene, o-dichlorobenzene, p-dichlorobenzene, m-dichlorobenzene, 1,2, 3-trichlorobenzene, 1,2, 4-trichlorobenzene, bromobenzene and dibromobenzene.
3. The method for preparing the carbon quantum dot modified perovskite solar cell as claimed in claim 1, wherein the wavelength of the pulse laser in S1 is one of 266nm, 355nm, 532nm and 1064nm, the energy is 50-1000 mJ/pulse, the irradiation time is 1-60min, and the size of the prepared carbon quantum dot is 3-10 nm.
4. the method according to claim 1, wherein the perovskite precursors of S2 are AX and BX2A compound of the formula (I), wherein A is CH3NH3 +、HC(＝NH)NH2 +、Cs+、Rb+、K+b is Pb2 +，Sn2 +X is one or more of halide ions.
5. the preparation method of the carbon quantum dot modified perovskite solar cell as claimed in claim 1, wherein in S2, a perovskite precursor solution is spin-coated on a transparent conductive substrate covered with an electron transport layer, two steps of spin coating are adopted, namely low-speed 2000rpm/10S and high-speed 4000rpm/30S, the carbon quantum dot solution prepared in S1 is dropwise added when the high-speed spin coating is carried out for the remaining 5-10S, the carbon quantum dot modified perovskite thin film is prepared after heat treatment at 100 ℃ for 10-90min, the concentration of the perovskite precursor solution is 1.2mol/L, the concentration of the carbon quantum dot solution is 0.1-1mg/mL, the ratio of the volume of the perovskite precursor solution to the volume of the carbon quantum dot solution is 1:8, and the thickness of the thin film is 300-700 nm.
6. the method according to claim 1, wherein the transparent conductive matrix in S2 is one of fluorine-doped tin dioxide, indium tin oxide, and a flexible matrix.
7. The method according to claim 1, wherein the electron transport layer in S2 is one or more of titanium dioxide, tin dioxide, zinc oxide, and [6,6] -phenylcarbon-6-methyl butyrate, and the thickness of the electron transport layer is 30-100 nm.
8. The method for preparing a carbon quantum dot modified perovskite solar cell as claimed in claim 1, wherein the hole transport layer in S2 is made of one of 2,2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene, poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine ], poly (3-hexylthiophene-2, 5-diyl), polyethylenedioxythiophene-poly (styrenesulfonate) and cuprous thiocyanate, and the thickness of the hole transport layer is 100-200 nm.
9. The method according to claim 1, wherein the metal electrode in S2 is one of gold, silver and aluminum, and the thickness of the metal electrode is 60-120 nm.
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