CN108878661A - A kind of preparation method of the perovskite solar battery of carbon quantum dot modification - Google Patents
A kind of preparation method of the perovskite solar battery of carbon quantum dot modification Download PDFInfo
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- CN108878661A CN108878661A CN201810696864.XA CN201810696864A CN108878661A CN 108878661 A CN108878661 A CN 108878661A CN 201810696864 A CN201810696864 A CN 201810696864A CN 108878661 A CN108878661 A CN 108878661A
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- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
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- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
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Abstract
The invention belongs to technical field of solar batteries, are related to a kind of preparation method of the perovskite solar battery of carbon quantum dot modification.The preparation method includes：Carbon quantum dot solution is prepared in situ out using pulse laser irradiation anti-solvent；Then perovskite precursor solution is spun on the electrically conducting transparent matrix for being covered with electron transfer layer, drips to carbon quantum dot solution on perovskite thin film in spin coating process, form the perovskite thin film of carbon quantum dot modification after heat treatment；Hole transmission layer and metal electrode are finally prepared, the preparation of perovskite solar battery is completed.The carbon quantum dot size of this method preparation is controllable, dispersibility and excellent in stability, can be introduced directly into perovskite thin film, help to simplify perovskite preparation process.Carbon quantum dot prepared by the present invention modification perovskite solar cell photoelectric high conversion efficiency, stability are good, and efficiency reaches as high as 21% or more, has high practical application value.
Description
Technical field
The invention belongs to technical field of solar batteries, are related to a kind of perovskite solar battery of carbon quantum dot modification
Preparation method.
Background technique
Effect is converted in the perovskite solar cell photoelectric of photovoltaic art, the hybrid inorganic-organic of low temperature solution polycondensation preparation
Rate alreadys exceed 20%, can almost compare favourably with monocrystaline silicon solar cell.This most significant advantage of low-temperature fabrication
It exactly can simplify battery preparation technique, improve film quality.However, the polycrystalline perovskite thin film of low temperature solution polycondensation preparation is in table
There are a large amount of defect, these defects will lead to carrier non-radiative recombination and accelerate moisture and oxygen to thin for face and grain boundaries
The degeneration of film, to reduce the performance of battery.How to enhance stability again while improving battery efficiency becomes one ten
Divide crucial problem.
Small organic molecule or polymer are carried to be passivated perovskite surface and interface defect by anti-solvent, are current perovskites
The most common method of modified film.However, most of small molecule compound and polymer conductivity are poor, it is unfavorable for perovskite photoproduction
Carrier mobility.Quantum dot especially carbon quantum dot size itself is small and has high conductivity and high mobility, is very suitable to modify
Perovskite surface and crystal boundary, facilitate the extraction and transmission of perovskite photo-generated carrier, to improve perovskite solar battery
Photoelectric conversion efficiency.However, major part carbon quantum dot is synthesized by chemical method at present, this technique is lacked there are some
It falls into：Such as period is long, technique is cumbersome, at high cost, size is inhomogenous, and since bad dispersibility is difficult to directly in the perovskite sun
It can be utilized in battery.Seek based on cheap raw material, size is controllable, technique simplifies carbon quantum dot preparation for exploitation high efficiency and
Stable perovskite solar battery is of great significance.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of the perovskite solar battery of carbon quantum dot modification, to solve
The problem of proposed in above-mentioned background technique.
The technical scheme adopted by the invention is that a kind of preparation side of the perovskite solar battery of carbon quantum dot modification
Method, this method are specifically to follow the steps below：
The preparation of S1, carbon quantum dot solution：In anhydrous and oxygen-free environment, carbon is prepared by pulse laser irradiation anti-solvent
Quantum dot solution；
The preparation for the perovskite solar battery that S2, carbon quantum dot are modified：In the electrically conducting transparent for being covered with electron transfer layer
It is thin to perovskite to be introduced into carbon quantum dot solution prepared in S1 in spin coating process for spin coating perovskite precursor solution on matrix
On film, the perovskite thin film of carbon quantum dot modification is formed after heat treatment, then in the perovskite thin film spin coating of carbon quantum dot modification
Hole transmission layer, finally hot evaporation metal electrode on the hole transport layer, is prepared the perovskite sun of carbon quantum dot modification
It can battery.
Further, anti-solvent is benzene kind solvent in S1, be toluene, ethylbenzene, ortho-xylene, paraxylene, meta-xylene,
One of chlorobenzene, o-dichlorohenzene, paracide, m-dichlorobenzene, 1,2,3- trichloro-benzenes, 1,2,4- trichloro-benzenes, bromobenzene, dibromobenzene
Or a variety of, preferably chlorobenzene or toluene.
Further, the wavelength of pulse laser is 266nm, 355nm, one of 532nm and 1064nm in S1, and energy is
50~1000mJ/ pulse, irradiation time 1-60min, prepared carbon quantum dot is having a size of 3-10nm.
Further, perovskite presoma is AX and BX in S22Type compound, wherein A is CH3NH3 +, HC (=NH) NH2 +、
Cs+、Rb+、K+One of or a variety of, B Pb2 +, Sn2 +One of or it is a variety of, X is one of halide ion or a variety of,
AX type compounds precursors are preferably CH3NH3Br, HC (=NH) NH3I, one of CsI or a variety of, BX2Type compound forerunner
Body is preferably PbI2、BrI2One of or it is a variety of.
Further, the electrically conducting transparent matrix for being covered with electron transfer layer is by the spin coating electronics on electrically conducting transparent matrix
Transport layer and obtain, perovskite precursor solution is spun in S2 on the electrically conducting transparent matrix for be covered with electron transfer layer using low
Carbon prepared in S1 is added dropwise when high speed spin coating 5~10s of residue for two step spin coating of fast 2000rpm/10s and high speed 4000rpm/30s
Quantum dot solution, 100 DEG C heat treatment 10-90min after prepare carbon quantum dot modification perovskite thin film, the perovskite forerunner
The ratio of liquid solution and carbon quantum dot solution usage amount be 0.1mg/mL-1mg/mL, the film with a thickness of 300-700nm.
Further, electrically conducting transparent matrix is one in the stannic oxide, tin indium oxide, flexible substrate of Fluorin doped in S2
Kind.
Further, electron transport layer materials are titanium dioxide, stannic oxide, zinc oxide, [6,6]-phenyl carbons 6- in S2
One or more of methyl butyrate, preferably titanium dioxide, electron transfer layer with a thickness of 30-100nm.
Further, the material of S2 hole-transporting layer is 2,2', 7,7'- tetra- [N, N- bis- (4- methoxyphenyl) ammonia
Base] -9,9'- spiral shell, two fluorenes, it is poly- [bis- (4- phenyl) (2,4,6- trimethylphenyl) amine], it is poly- (3- hexyl thiophene -2,5- diyl), gather
Ethylenedioxy thiophene-is poly- (styrene sulfonate), one of cuprous sulfocyanide, preferably 2,2', 7,7'- tetra- [bis- (4- of N, N-
Methoxyphenyl) amino] -9,9'- spiral shell, two fluorenes (Spiro-OMeTAD), hole transmission layer with a thickness of 100-200nm.
Further, in S2 metal electrode be one of gold, silver, aluminium, metal electrode with a thickness of 60-120nm, preferably
For 80nm.
The beneficial effects of the invention are as follows：(1) pulse laser irradiation anti-solvent method of the invention can directly prepare concentration,
Size is controllable, the carbon quantum dot of polymolecularity and stability, needs not move through the complicated technologies such as hydro-thermal, ligand exchange, centrifugal drying
Use can be direct plungeed into, compared with the carbon quantum made from the traditional preparation methods, good dispersion, stability is high；(2) present invention can
Carbon quantum dot solution is introduced directly into perovskite thin film spin coating preparation process, without individually preparing carbon quantum dot-anti-solvent
Solution can prepare the perovskite thin film of carbon quantum passivation, compared with existing carbon quantum dot modifies perovskite preparation method, technique
Simply, easy to operate, significant effect；(3) the perovskite thin film solar battery effect of the carbon quantum dot modification prepared by the present invention
Rate is high, stability is good, and incident photon-to-electron conversion efficiency increases to above 21% from the 15% of basis, substantially improves low temperature solution polycondensation preparation
Perovskite solar battery incident photon-to-electron conversion efficiency and stability, have high application prospect.
Detailed description of the invention
Fig. 1 is the perovskite solar battery structure schematic diagram of carbon quantum dot of the present invention modification；
Fig. 2 is carbon quantum dot transmission electron microscope photo prepared by embodiment 1；
Fig. 3 is that the current-voltage of carbon quantum dot modification and unmodified perovskite solar battery prepared by embodiment 1 is bent
Line chart；
Fig. 4 is carbon quantum dot transmission electron microscope photo prepared by embodiment 2；
Fig. 5 is the current -voltage curve figure of the perovskite solar battery of carbon quantum dot modification prepared by embodiment 2；
Fig. 6 is carbon quantum dot transmission electron microscope photo prepared by embodiment 3；
Fig. 7 is the current -voltage curve figure of the perovskite solar battery of carbon quantum dot modification prepared by embodiment 3；
Fig. 8 is carbon quantum dot transmission electron microscope photo prepared by embodiment 4；
Fig. 9 is the current -voltage curve figure of the perovskite solar battery of carbon quantum dot modification prepared by embodiment 4；
Figure 10 is carbon quantum dot transmission electron microscope photo prepared by embodiment 5；
Figure 11 is the current -voltage curve figure of the perovskite solar battery of carbon quantum dot modification prepared by embodiment 5；
Figure 12 is carbon quantum dot transmission electron microscope photo prepared by embodiment 6；
Figure 13 is the current -voltage curve figure of the perovskite solar battery of carbon quantum dot modification prepared by embodiment 6.
Description of symbols：
1. electrically conducting transparent matrix；2. electron transfer layer；3. perovskite-carbon quantum dot composite layer；4. carbon quantum dot；5. hole
Transport layer；6. metal electrode.
Specific embodiment
Technical scheme is described further combined with specific embodiments below, it is to be understood that guarantor of the invention
Shield range is not limited by specific embodiment.The Applicant declares that the above embodiment is a preferred embodiment of the present invention, but this
The embodiment of invention is simultaneously not restricted to the described embodiments, and others are any without departing from the spirit and principles of the present invention
Made laser energy, wavelength shift, anti-solvent replacement, combination, perovskite component changes and carbon quantum dot introduction volume, time
It should be equivalent substitute mode, be included within the scope of the present invention.
Embodiment 1
A kind of preparation method of the perovskite solar battery of carbon quantum dot modification, this method is specifically according to the following steps
It carries out：
It is S1, anti-with the chlorobenzene for the pulse laser irradiation 6mL that wavelength is 355nm, energy is 100mJ under the conditions of anhydrous and oxygen-free
Solvent 10min is prepared having a size of 3nm or so, the carbon quantum dot that concentration is 0.1mg/mL, as shown in Fig. 2 transmission electron microscope photo；
S2, selection sheet resistance are 15 Ω/sq, with a thickness of 2.2mm, the FTO glass (SnO of Fluorin doped that transmitance is 84.5%2
Transparent conducting glass) it is conducting base, FTO glass is successively cleaned by ultrasonic in glass cleaner, acetone, dehydrated alcohol
Glass after drying is cleaned in ozone plasma cleaning machine 15min, removes glass table by 20min later with being dried with nitrogen
Face organic matter and the hydrophily for enhancing surface；
S3, TiO is selected2As the electron transfer layer of perovskite solar battery：Take bis- (levulinic ketone group) diisopropyls
100 μ L of titanate esters and isopropanol 1mL are mixed and stirred for 2h, and the mixed solution after stirring is filtered for use, takes 50 μ L prepared
TiO2Presoma drips to the FTO spin-on-glass of surface treatment, revolving speed 2000r/min, spin-coating time 60s, after spin coating
Glass, which is placed on warm table, is heat-treated 10min at 150 DEG C, is then placed in batch-type furnace and keeps the temperature 60min at 500 DEG C of high temperature, system
For out with a thickness of 50nm densification TiO2Layer；
S4, the Cs that 1.2mol/L is prepared in argon gas glove box0.05FA0.81MA0.14PbI2.55Br0.45Perovskite presoma：
Take 15.6mg CH3NH3I, 166.6mg HC (=NH) NH3I, 19.1mg CH3NH3Br, 474.4mg PbI2And 62.8mg
PbBr2800 μ L dimethylformamides and 200 μ L dimethyl sulfoxides are mixed and added into small reagent bottle, by mixed solution 60
Stir 2h at DEG C, organic filter head be filtered obtain 1mL for experiment 1.2mol/L perovskite precursor solution；
S5, the 25 μ l perovskite precursor solution is taken to drip to 15 × 15mm2Overlay electronic transport layer TiO2FTO matrix
On, low speed (2000rmp) spin coating 10s, high speed (4000rmp) spin coating 30s drips off 200 μ l steps in remaining 10s in three seconds
Carbon quantum dot solution prepared by S1,100 DEG C of heat treatment 1h, prepares surface uniform ground, the carbon quantum dot with a thickness of 600nm
The perovskite thin film of modification；
S6, one layer of hole transmission layer Spiro-OMeTAD of spin coating on the perovskite thin film of preparation carbon quantum dot modification are thick
Degree is 150nm, aoxidizes 12h in air；
S7, vapor deposition one level product are 0.1cm2, with a thickness of 80nm Au electrode to get to carbon quantum dot modification perovskite
The structural schematic diagram of solar battery, perovskite solar battery is specifically as shown in Figure 1.
The highest incident photon-to-electron conversion efficiency for measuring the battery is 18.79%, and not plus the battery peak efficiency of carbon quantum dot is
17.45%, as shown in Figure 3.
Embodiment 2
The preparation method of the perovskite solar battery of a kind of carbon quantum dot modification, which is characterized in that this method is specifically
It follows the steps below：
It is S1, anti-with the chlorobenzene for the pulse laser irradiation 6mL that wavelength is 355nm, energy is 100mJ under the conditions of anhydrous and oxygen-free
Solvent 30min is prepared having a size of 3nm or so, the carbon quantum dot that concentration is 0.6mg/mL, as shown in Fig. 4 transmission electron microscope photo,
Compared with Example 1, the carbon quantum dot size constancy, concentration increase；
S2, selection sheet resistance are 15 Ω/sq, and with a thickness of 2.2mm, the FTO glass that transmitance is 84.5% is conducting base, will
FTO glass is successively in glass cleaner, acetone, is cleaned by ultrasonic 20min in dehydrated alcohol, later with being dried with nitrogen, after drying
Glass clean 15min in ozone plasma cleaning machine, remove glass surface organic matter and enhance the hydrophily on surface；
S3, TiO is selected2As the electron transfer layer of perovskite solar battery：Take bis- (levulinic ketone group) diisopropyls
100 μ L of titanate esters and isopropanol 1mL are mixed and stirred for 2h, and the mixed solution after stirring is filtered for use, takes 50 μ L prepared
TiO2Presoma drips to the FTO spin-on-glass of surface treatment, revolving speed 2000r/min, spin-coating time 60s, after spin coating
Glass, which is placed on warm table, is heat-treated 10min at 150 DEG C, is then placed in batch-type furnace and keeps the temperature 60min at 500 DEG C of high temperature, system
For out with a thickness of 50nm densification TiO2Layer；
S4, the Cs that 1.2mol/L is prepared in argon gas glove box0.05FA0.81MA0.14PbI2.55Br0.45Perovskite presoma：
Take 15.6mg CH3NH3I, 166.6mg HC (=NH) NH3I, 19.1mg CH3NH3Br, 474.4mg PbI2And 62.8mg
PbBr2800 μ L dimethylformamides and 200 μ L dimethyl sulfoxides are mixed and added into small reagent bottle, by mixed solution 60
Stir 2h at DEG C, organic filter head be filtered obtain 1mL for experiment 1.2mol/L perovskite precursor solution；
S5, the 25 μ l perovskite presoma is taken to drip to 15 × 15mm2Overlay electronic transport layer TiO2FTO matrix on, it is low
It is made to drip off 200 μ l step S1 in remaining 10s by speed (2000rmp) spin coating 10s, high speed (4000rmp) spin coating 30s in three seconds
Standby carbon quantum dot solution, 100 DEG C of heat treatment 1h, prepare surface uniform ground, with a thickness of 600nm carbon quantum dot modify
Perovskite thin film；
S6, one layer of hole transmission layer Spiro-OMeTAD of spin coating on the perovskite thin film of preparation carbon quantum dot modification are thick
Degree is 150nm, aoxidizes 12h in air；
S7, vapor deposition one level product are 0.1cm2, with a thickness of 80nm Au electrode to get to carbon quantum dot modification perovskite
Solar battery.
The highest incident photon-to-electron conversion efficiency for measuring the battery is 19.74%, as shown in Figure 5.
Embodiment 3
The preparation method of the perovskite solar battery of a kind of carbon quantum dot modification, which is characterized in that this method is specifically
It follows the steps below：
It is S1, anti-with the chlorobenzene for the pulse laser irradiation 6mL that wavelength is 355nm, energy is 200mJ under the conditions of anhydrous and oxygen-free
Solvent 30min is prepared having a size of 5nm or so, the carbon quantum dot that concentration is 0.6mg/mL, as shown in Fig. 6 transmission electron microscope photo,
Compared with Example 2, which increases, and concentration is constant；
S2, selection sheet resistance are 15 Ω/sq, and with a thickness of 2.2mm, the FTO glass that transmitance is 84.5% is conducting base, will
FTO glass is successively in glass cleaner, acetone, is cleaned by ultrasonic 20min in dehydrated alcohol, later with being dried with nitrogen, after drying
Glass clean 15min in ozone plasma cleaning machine, remove glass surface organic matter and enhance the hydrophily on surface；
S3, TiO is selected2As the electron transfer layer of perovskite solar battery：Take bis- (levulinic ketone group) diisopropyls
100 μ L of titanate esters and isopropanol 1mL are mixed and stirred for 2h, and the mixed solution after stirring is filtered for use, takes 50 μ L prepared
TiO2Presoma drips to the FTO spin-on-glass of surface treatment, revolving speed 2000r/min, spin-coating time 60s, after spin coating
Glass, which is placed on warm table, is heat-treated 10min at 150 DEG C, is then placed in batch-type furnace and keeps the temperature 60min at 500 DEG C of high temperature, system
For out with a thickness of 50nm densification TiO2Layer；
S4, the Cs that 1.2mol/L is prepared in argon gas glove box0.05FA0.81MA0.14PbI2.55Br0.45Perovskite presoma：
Take 15.6mg CH3NH3I, 166.6mg HC (=NH) NH3I, 19.1mg CH3NH3Br, 474.4mg PbI2And 62.8mg
PbBr2800 μ L dimethylformamides and 200 μ L dimethyl sulfoxides are mixed and added into small reagent bottle, by mixed solution 60
Stir 2h at DEG C, organic filter head be filtered obtain 1mL for experiment 1.2mol/L perovskite precursor solution；
S5, the 25 μ l perovskite presoma is taken to drip to 15 × 15mm2Overlay electronic transport layer TiO2FTO matrix on, it is low
It is made to drip off 200 μ l step S1 in remaining 10s by speed (2000rmp) spin coating 10s, high speed (4000rmp) spin coating 30s in three seconds
Standby carbon quantum dot solution, 100 DEG C of heat treatment 1h, prepare surface uniform ground, with a thickness of 600nm carbon quantum dot modify
Perovskite thin film；
S6, one layer of hole transmission layer Spiro-OMeTAD of spin coating on the perovskite thin film of preparation carbon quantum dot modification are thick
Degree is 150nm, aoxidizes 12h in air；
S7, vapor deposition one level product are 0.1cm2, with a thickness of 80nm Au electrode to get to carbon quantum dot modification perovskite
Solar battery.
The highest incident photon-to-electron conversion efficiency for measuring the battery is 21.09%, as shown in Figure 7.
Embodiment 4
The preparation method of the perovskite solar battery of a kind of carbon quantum dot modification, which is characterized in that this method is specifically
It follows the steps below：
It is S1, anti-with the chlorobenzene for the pulse laser irradiation 6mL that wavelength is 355nm, energy is 400mJ under the conditions of anhydrous and oxygen-free
Solvent 30min is prepared having a size of 10nm or so, the carbon quantum dot that concentration is 0.6mg/mL, such as Fig. 8 transmission electron microscope photo institute
Show, compared with Example 3, which increases, and concentration is constant；
S2, selection sheet resistance are 15 Ω/sq, and with a thickness of 2.2mm, the FTO glass that transmitance is 84.5% is conducting base, will
FTO glass is successively in glass cleaner, acetone, is cleaned by ultrasonic 20min in dehydrated alcohol, later with being dried with nitrogen, after drying
Glass clean 15min in ozone plasma cleaning machine, remove glass surface organic matter and enhance the hydrophily on surface；
S3, TiO is selected2As the electron transfer layer of perovskite solar battery：Take bis- (levulinic ketone group) diisopropyls
100 μ L of titanate esters and isopropanol 1mL are mixed and stirred for 2h, and the mixed solution after stirring is filtered for use, takes 50 μ L prepared
TiO2Presoma drips to the FTO spin-on-glass of surface treatment, revolving speed 2000r/min, spin-coating time 60s, after spin coating
Glass, which is placed on warm table, is heat-treated 10min at 150 DEG C, is then placed in batch-type furnace and keeps the temperature 60min at 500 DEG C of high temperature, system
For out with a thickness of 50nm densification TiO2Layer；
S4, the Cs that 1.2mol/L is prepared in argon gas glove box0.05FA0.81MA0.14PbI2.55Br0.45Perovskite presoma：
Take 15.6mg CH3NH3I, 166.6mg HC (=NH) NH3I, 19.1mg CH3NH3Br, 474.4mg PbI2And 62.8mg
PbBr2800 μ L dimethylformamides and 200 μ L dimethyl sulfoxides are mixed and added into small reagent bottle, by mixed solution 60
Stir 2h at DEG C, organic filter head be filtered obtain 1mL for experiment 1.2mol/L perovskite precursor solution；
S5, the 25 μ l perovskite presoma is taken to drip to 15 × 15mm2Overlay electronic transport layer TiO2FTO matrix on, it is low
It is made to drip off 200 μ l step S1 in remaining 10s by speed (2000rmp) spin coating 10s, high speed (4000rmp) spin coating 30s in three seconds
Standby carbon quantum dot solution, 100 DEG C of heat treatment 1h, prepare surface uniform ground, with a thickness of 600nm carbon quantum dot modify
Perovskite thin film；
S6, one layer of hole transmission layer Spiro-OMeTAD of spin coating on the perovskite thin film of preparation carbon quantum dot modification are thick
Degree is 150nm, aoxidizes 12h in air；
S7, vapor deposition one level product are 0.1cm2, with a thickness of 80nm Au electrode to get to carbon quantum dot modification perovskite
Solar battery.
The highest incident photon-to-electron conversion efficiency for measuring the battery is 18.28%, as shown in Figure 9.
Embodiment 5
The preparation method of the perovskite solar battery of a kind of carbon quantum dot modification, which is characterized in that this method is specifically
It follows the steps below：
It is S1, anti-with the chlorobenzene for the pulse laser irradiation 6mL that wavelength is 532nm, energy is 200mJ under the conditions of anhydrous and oxygen-free
Solvent 30min is prepared having a size of 5nm or so, the carbon quantum dot that concentration is 0.8mg/mL, such as Figure 10 transmission electron microscope photo institute
Show, compared with Example 3, the carbon quantum dot size constancy, concentration increases；
S2, selection sheet resistance are 15 Ω/sq, and with a thickness of 2.2mm, the FTO glass that transmitance is 84.5% is conducting base, will
FTO glass is successively in glass cleaner, acetone, is cleaned by ultrasonic 20min in dehydrated alcohol, later with being dried with nitrogen, after drying
Glass clean 15min in ozone plasma cleaning machine, remove glass surface organic matter and enhance the hydrophily on surface；
S3, TiO is selected2As the electron transfer layer of perovskite solar battery：Take bis- (levulinic ketone group) diisopropyls
100 μ L of titanate esters and isopropanol 1mL are mixed and stirred for 2h, and the mixed solution after stirring is filtered for use, takes 50 μ L prepared
TiO2Presoma drips to the FTO spin-on-glass of surface treatment, revolving speed 2000r/min, spin-coating time 60s, after spin coating
Glass, which is placed on warm table, is heat-treated 10min at 150 DEG C, is then placed in batch-type furnace and keeps the temperature 60min at 500 DEG C of high temperature, system
For out with a thickness of 50nm densification TiO2Layer；
S4, the Cs that 1.2mol/L is prepared in argon gas glove box0.05FA0.81MA0.14PbI2.55Br0.45Perovskite presoma：
Take 15.6mg CH3NH3I, 166.6mg HC (=NH) NH3I, 19.1mg CH3NH3Br, 474.4mg PbI2And 62.8mg
PbBr2800 μ L dimethylformamides and 200 μ L dimethyl sulfoxides are mixed and added into small reagent bottle, by mixed solution 60
Stir 2h at DEG C, organic filter head be filtered obtain 1mL for experiment 1.2mol/L perovskite precursor solution；
S5, the 25 μ l perovskite presoma is taken to drip to 15 × 15mm2Overlay electronic transport layer TiO2FTO matrix on, it is low
It is made to drip off 200 μ l step S1 in remaining 10s by speed (2000rmp) spin coating 10s, high speed (4000rmp) spin coating 30s in three seconds
Standby carbon quantum dot solution, 100 DEG C of heat treatment 1h, prepare surface uniform ground, with a thickness of 600nm carbon quantum dot modify
Perovskite thin film；
S6, one layer of hole transmission layer Spiro-OMeTAD of spin coating on the perovskite thin film of preparation carbon quantum dot modification are thick
Degree is 150nm, aoxidizes 12h in air；
S7, vapor deposition one level product are 0.1cm2, with a thickness of 80nm Au electrode to get to carbon quantum dot modification perovskite
Solar battery.
The highest incident photon-to-electron conversion efficiency for measuring the battery is 19.82%, as shown in figure 11.
Embodiment 6
The preparation method of the perovskite solar battery of a kind of carbon quantum dot modification, which is characterized in that this method is specifically
It follows the steps below：
S1, under the conditions of anhydrous and oxygen-free with the chlorobenzene for the pulse laser irradiation 6mL that wavelength is 1064nm, energy is 200mJ
Anti-solvent 30min is prepared having a size of 5nm or so, the carbon quantum dot that concentration is 1mg/mL, such as Figure 12 transmission electron microscope photo institute
Show, compared with Example 3, which increases, and concentration increases；
S2, selection sheet resistance are 15 Ω/sq, and with a thickness of 2.2mm, the FTO glass that transmitance is 84.5% is conducting base, will
FTO glass is successively in glass cleaner, acetone, is cleaned by ultrasonic 20min in dehydrated alcohol, later with being dried with nitrogen, after drying
Glass clean 15min in ozone plasma cleaning machine, remove glass surface organic matter and enhance the hydrophily on surface；
S3, TiO is selected2As the electron transfer layer of perovskite solar battery：Take bis- (levulinic ketone group) diisopropyls
100 μ L of titanate esters and isopropanol 1mL are mixed and stirred for 2h, and the mixed solution after stirring is filtered for use, takes 50 μ L prepared
TiO2Presoma drips to the FTO spin-on-glass of surface treatment, revolving speed 2000r/min, spin-coating time 60s, after spin coating
Glass, which is placed on warm table, is heat-treated 10min at 150 DEG C, is then placed in batch-type furnace and keeps the temperature 60min at 500 DEG C of high temperature, system
For out with a thickness of 50nm densification TiO2Layer；
S4, the Cs that 1.2mol/L is prepared in argon gas glove box0.05FA0.81MA0.14PbI2.55Br0.45Perovskite presoma：
Take 15.6mg CH3NH3I, 166.6mg HC (=NH) NH3I, 19.1mg CH3NH3Br, 474.4mg PbI2And 62.8mg
PbBr2800 μ L dimethylformamides and 200 μ L dimethyl sulfoxides are mixed and added into small reagent bottle, by mixed solution 60
Stir 2h at DEG C, organic filter head be filtered obtain 1mL for experiment 1.2mol/L perovskite precursor solution；
S5, the 25 μ l perovskite presoma is taken to drip to 15 × 15mm2Overlay electronic transport layer TiO2FTO matrix on, it is low
It is made to drip off 200 μ l step S1 in remaining 10s by speed (2000rmp) spin coating 10s, high speed (4000rmp) spin coating 30s in three seconds
Standby carbon quantum dot solution, 100 DEG C of heat treatment 1h, prepare surface uniform ground, with a thickness of 600nm carbon quantum dot modify
Perovskite thin film；
S6, one layer of hole transmission layer Spiro-OMeTAD of spin coating on the perovskite thin film of preparation carbon quantum dot modification are thick
Degree is 150nm, aoxidizes 12h in air；
S7, vapor deposition one level product are 0.1cm2, with a thickness of 80nm Au electrode to get to carbon quantum dot modification perovskite
Solar battery.
The highest incident photon-to-electron conversion efficiency for measuring the battery is 17.1%, as shown in figure 13.
Disclosed above is only specific embodiments of the present invention, and still, the embodiment of the present invention is not limited to this, Ren Heben
What the technical staff in field can think variation should all fall into protection scope of the present invention.
Claims (9)
1. a kind of preparation method of the perovskite solar battery of carbon quantum dot modification, which is characterized in that this method is specifically to press
It is carried out according to following steps：
The preparation of S1, carbon quantum dot solution：In anhydrous and oxygen-free environment, carbon quantum is prepared by pulse laser irradiation anti-solvent
Point solution；
The preparation for the perovskite solar battery that S2, carbon quantum dot are modified：In the electrically conducting transparent matrix for being covered with electron transfer layer
Upper spin coating perovskite precursor solution is introduced into carbon quantum dot solution prepared in S1 to perovskite thin film in spin coating process
On, the perovskite thin film of carbon quantum dot modification is formed after heat treatment, then the spin coating on the perovskite thin film of carbon quantum dot modification
Hole transmission layer, finally hot evaporation metal electrode on the hole transport layer, is prepared the perovskite sun of carbon quantum dot modification
It can battery.
2. a kind of preparation method of the perovskite solar battery of carbon quantum dot modification as described in claim 1, feature exist
In anti-solvent described in S1 is benzene kind solvent, is toluene, ethylbenzene, ortho-xylene, paraxylene, meta-xylene, chlorobenzene, neighbour two
One of chlorobenzene, paracide, m-dichlorobenzene, 1,2,3- trichloro-benzenes, 1,2,4- trichloro-benzenes, bromobenzene, dibromobenzene are a variety of.
3. a kind of preparation method of the perovskite solar battery of carbon quantum dot modification as described in claim 1, feature exist
In the wavelength of pulse laser described in S1 is 266nm, 355nm, one of 532nm and 1064nm, energy 50-1000mJ/
Pulse, irradiation time 1-60min, prepared carbon quantum dot is having a size of 3-10nm.
4. a kind of preparation method of the perovskite solar battery of carbon quantum dot modification as described in claim 1, feature exist
In perovskite presoma described in S2 is AX and BX2Type compound, wherein A is CH3NH3 +, HC (=NH) NH2 +、Cs+、Rb+、K+
One of or a variety of, B Pb2 +, Sn2 +One of or it is a variety of, X is one of halide ion or a variety of.
5. a kind of preparation method of the perovskite solar battery of carbon quantum dot modification as described in claim 1, feature exist
In perovskite precursor solution being spun in S2 on the electrically conducting transparent matrix for be covered with electron transfer layer using low speed
Carbon amounts prepared in S1 is added dropwise when high speed spin coating 5~10s of residue for two step spin coating of 2000rpm/10s and high speed 4000rpm/30s
Son puts solution, and the perovskite thin film of carbon quantum dot modification, the perovskite presoma are prepared after 100 DEG C of heat treatment 10-90min
The ratio of solution and carbon quantum dot solution usage amount be 0.1mg/mL-1mg/mL, the film with a thickness of 300-700nm.
6. a kind of preparation method of the perovskite solar battery of carbon quantum dot modification as described in claim 1, feature exist
In electrically conducting transparent matrix described in S2 is one of stannic oxide, tin indium oxide, flexible substrate of Fluorin doped.
7. a kind of preparation method of the perovskite solar battery of carbon quantum dot modification as described in claim 1, feature exist
In electron transport layer materials described in S2 are titanium dioxide, in stannic oxide, zinc oxide, [6,6]-phenyl carbons 6- methyl butyrate
One or more, the electron transfer layer with a thickness of 30-100nm.
8. a kind of preparation method of the perovskite solar battery of carbon quantum dot modification as described in claim 1, feature exist
In the material of hole transmission layer described in S2 is 2,2', 7,7'- tetra- [N, N- bis- (4- methoxyphenyl) amino] -9,9'- spiral shells two
Fluorenes, poly- [bis- (4- phenyl) (2,4,6- trimethylphenyl) amine], poly- (3- hexyl thiophene -2,5- diyl), Polyglycolic acid fibre -
Poly- (styrene sulfonate), one of cuprous sulfocyanide, the hole transmission layer with a thickness of 100-200nm.
9. a kind of preparation method of the perovskite solar battery of carbon quantum dot modification as described in claim 1, feature exist
In, metal electrode described in S2 be one of gold, silver, aluminium, the metal electrode with a thickness of 60-120nm.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110492004A (en) * | 2019-07-31 | 2019-11-22 | 北京科技大学 | A kind of perovskite preparation method of solar battery of carbon quantum dot modification calcium titanium ore bed |
| CN110649163A (en) * | 2019-09-30 | 2020-01-03 | 吉林师范大学 | Perovskite solar cell with sandwich structure electron transport layer and preparation method |
| CN110739401A (en) * | 2019-10-18 | 2020-01-31 | 信阳师范学院 | method for improving photoelectric conversion efficiency of perovskite thin-film solar cell |
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| CN113258007A (en) * | 2021-05-08 | 2021-08-13 | 华能新能源股份有限公司 | Carbon quantum dot, preparation method thereof and application of carbon quantum dot in perovskite solar cell |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104087296A (en) * | 2014-07-08 | 2014-10-08 | 合肥工业大学 | Method for preparing fluorescent carbon quantum dots by laser irradiation |
| CN105047417A (en) * | 2015-06-29 | 2015-11-11 | 中南大学 | Quantum dot perovskite co-sensitization solar cell and preparation method thereof |
| US20170110672A1 (en) * | 2015-10-20 | 2017-04-20 | Korea Institute Of Science And Technology | N-doped nanocarbon materials and method for manufacturing the same |
| CN107134529A (en) * | 2017-03-27 | 2017-09-05 | 中山大学 | It is a kind of with perovskite solar cell of carbon nano dot modifying interface and preparation method thereof |
| CN107565025A (en) * | 2017-08-22 | 2018-01-09 | 东莞市联洲知识产权运营管理有限公司 | A kind of CH of carbon containing quantum dot3NH3BiI3The preparation method of based perovskite solar cell |
| CN107895759A (en) * | 2017-11-13 | 2018-04-10 | 济南大学 | A kind of preparation method that the efficient perovskite solar cell of PCBM electron transfer layers is adulterated using carbon quantum dot |
| CN107936942A (en) * | 2017-12-04 | 2018-04-20 | 合肥工业大学 | A kind of carbon-coated carbon gadolinium quantum dot and preparation method thereof |
-
2018
- 2018-06-29 CN CN201810696864.XA patent/CN108878661B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104087296A (en) * | 2014-07-08 | 2014-10-08 | 合肥工业大学 | Method for preparing fluorescent carbon quantum dots by laser irradiation |
| CN105047417A (en) * | 2015-06-29 | 2015-11-11 | 中南大学 | Quantum dot perovskite co-sensitization solar cell and preparation method thereof |
| US20170110672A1 (en) * | 2015-10-20 | 2017-04-20 | Korea Institute Of Science And Technology | N-doped nanocarbon materials and method for manufacturing the same |
| CN107134529A (en) * | 2017-03-27 | 2017-09-05 | 中山大学 | It is a kind of with perovskite solar cell of carbon nano dot modifying interface and preparation method thereof |
| CN107565025A (en) * | 2017-08-22 | 2018-01-09 | 东莞市联洲知识产权运营管理有限公司 | A kind of CH of carbon containing quantum dot3NH3BiI3The preparation method of based perovskite solar cell |
| CN107895759A (en) * | 2017-11-13 | 2018-04-10 | 济南大学 | A kind of preparation method that the efficient perovskite solar cell of PCBM electron transfer layers is adulterated using carbon quantum dot |
| CN107936942A (en) * | 2017-12-04 | 2018-04-20 | 合肥工业大学 | A kind of carbon-coated carbon gadolinium quantum dot and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| SHUJIE ZHOU等: "Slow‐Photon‐Effect‐Induced Photoelectrical‐Conversion Efficiency Enhancement for Carbon‐Quantum‐Dot‐Sensitized Inorganic CsPbBr3 Inverse Opal Perovskite Solar Cells", 《ADVANCED MATERIALS》 * |
Cited By (13)
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|---|---|---|---|---|
| CN110492004A (en) * | 2019-07-31 | 2019-11-22 | 北京科技大学 | A kind of perovskite preparation method of solar battery of carbon quantum dot modification calcium titanium ore bed |
| CN110649163A (en) * | 2019-09-30 | 2020-01-03 | 吉林师范大学 | Perovskite solar cell with sandwich structure electron transport layer and preparation method |
| CN110739401A (en) * | 2019-10-18 | 2020-01-31 | 信阳师范学院 | method for improving photoelectric conversion efficiency of perovskite thin-film solar cell |
| CN111146343B (en) * | 2020-01-16 | 2022-05-17 | 吉林大学 | Perovskite solar cell based on molybdenum disulfide/carbon quantum dot interface layer and preparation method |
| CN111146343A (en) * | 2020-01-16 | 2020-05-12 | 吉林大学 | Perovskite solar cell based on molybdenum disulfide/carbon quantum dot interface layer and preparation method |
| CN111477740A (en) * | 2020-05-14 | 2020-07-31 | 天津理工大学 | Polymer/quantum dot film memristor capable of simulating nerve synapse and preparation method thereof |
| CN111477740B (en) * | 2020-05-14 | 2023-09-26 | 天津理工大学 | Polymer/quantum dot film memristor capable of simulating nerve synapses and preparation method thereof |
| CN113299838A (en) * | 2021-04-14 | 2021-08-24 | 西安石油大学 | Method for stabilizing interface of perovskite thin film and hole transport layer |
| CN113299838B (en) * | 2021-04-14 | 2022-10-04 | 西安石油大学 | Method for stabilizing interface of perovskite thin film and hole transport layer |
| CN113258007B (en) * | 2021-05-08 | 2023-04-07 | 华能新能源股份有限公司 | Carbon quantum dot, preparation method thereof and application of carbon quantum dot in perovskite solar cell |
| CN113258007A (en) * | 2021-05-08 | 2021-08-13 | 华能新能源股份有限公司 | Carbon quantum dot, preparation method thereof and application of carbon quantum dot in perovskite solar cell |
| CN115849382A (en) * | 2022-12-26 | 2023-03-28 | 山东理工昊明新能源有限公司 | Silicon material for photovoltaic power generation and preparation method thereof |
| CN115849382B (en) * | 2022-12-26 | 2023-07-21 | 山东理工职业学院 | Silicon material for photovoltaic power generation and preparation method thereof |
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