CN110444672B - Fullerene derivative, preparation method and application thereof - Google Patents

Fullerene derivative, preparation method and application thereof Download PDF

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CN110444672B
CN110444672B CN201910675143.5A CN201910675143A CN110444672B CN 110444672 B CN110444672 B CN 110444672B CN 201910675143 A CN201910675143 A CN 201910675143A CN 110444672 B CN110444672 B CN 110444672B
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fullerene derivative
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王涛
陈梦婷
王卉
王胖
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Wuhan University of Technology WUT
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Abstract

The invention provides a fullerene derivative, and a preparation method and application thereof. The fullerene derivative is applied to the preparation of the perovskite solar cell, effectively passivates defects, promotes more effective charge extraction at an interface, and can enable the transmission capability of electrons to be stronger, so as to improve the short-circuit current and the power conversion efficiency of a device.

Description

Fullerene derivative, preparation method and application thereof
Technical Field
The invention belongs to the field of organic-inorganic hybrid semiconductor thin-film solar cells, and particularly relates to a fullerene derivative, and a preparation method and application thereof.
Background
Although the perovskite type solar cell has great advantages in terms of energy conversion efficiency, there are still many problems to be solved, such as stability of the cell, life of the cell, and the like. In order to push the efficiency of perovskite solar cells to approach its limits, it is necessary to further study and eliminate the problems of perovskite light absorption layer and electron transport layer defects, and to improve the stability of the device while improving the efficiency. Improving the efficiency and stability of the perovskite solar cell device is an opportunity and challenge, and the problem solved by interface engineering adds assistance to the development of the perovskite solar cell.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a fullerene derivative, and a preparation method and application thereof.
A fullerene derivative having the structural formula:
Figure BDA0002143030480000011
wherein R is Cl or-CH3。
The preparation method of the fullerene derivative is characterized by comprising the following steps of:
step 1): sequentially mixing fullerene, cinnamaldehyde,
Figure BDA0002143030480000012
Adding magnesium perchlorate into an o-dichlorobenzene solvent according to the molar ratio of 1:10:10: 4; wherein R is Cl or-CH3；
Step 2): condensing and refluxing for 60min at 180 ℃ to obtain the fullerene derivative;
step 3): separating the fullerene derivative by adopting a column chromatography.
The application of the fullerene derivative is characterized in that the fullerene derivative is applied to modification of an interface between an electron transport layer and a perovskite light absorption layer of a perovskite solar cell.
The application of the fullerene derivative is characterized by comprising the following steps:
step a): sequentially and respectively ultrasonically cleaning and drying a conductive glass substrate by using deionized water, ethanol and isopropanol, and then irradiating by using ultraviolet light;
step b): manufacturing an electron transmission layer on a conductive glass substrate;
step c): spin-coating the fullerene derivative on the electron transport layer obtained in the step b), and forming an interface modification layer after annealing treatment;
step d): manufacturing a perovskite film on the interface modification layer obtained in the step c) to be used as a perovskite light absorption layer;
step e): manufacturing a hole transport layer on the perovskite light absorption layer;
step f): and carrying out vacuum evaporation on the metal electrode on the hole transport layer, thus finishing the preparation of the perovskite solar cell device.
Further, the application of the fullerene derivative is characterized by comprising the following steps:
step a): ultrasonically cleaning a conductive glass substrate with deionized water, ethanol and isopropanol for 10min in sequence, drying, and irradiating with ultraviolet light for 10-15 min;
step b): spin coating 40 μ L TiO 10mg/mL solution at 3000rpm2Spin coating the solution on a conductive glass substrate for 40s, and heat treating at 150 deg.C for 30min to obtain TiO2A thin film layer as an electron transport layer;
step c): dissolving the fullerene derivative in a carbon disulfide solvent to prepare a solution with the concentration of 3mg/mL-5mg/mL, then taking 30 mu L of the solution to spin-coat on the electron transmission layer at the rotating speed of 4000rpm-6000rpm for 30s, and then annealing at 100 ℃ for 10min to form an interface modification layer;
step d): by PbI2Preparing perovskite precursor solution with MAI according to the molar ratio of 1: 1; spin-coating 50 mu L of perovskite precursor solution on the interface modification layer at the rotating speed of 6000rpm for 15s, then reducing the rotating speed to 3700rpm, spin-coating 75 mu L and 34.5mg/mL of MAI isopropanol solution, maintaining the rotating speed for 45s, and then carrying out annealing treatment at 100 ℃ for 30min to obtain a perovskite thin film as a perovskite light absorption layer;
step e): weighing 80mg of Spiro-OMeTAD, dissolving in 1mL of chlorobenzene, fully dissolving, adding 17.5 mu L of Li-TFSI acetonitrile solution of 520mg/mL and 28.5 mu L of tributyl phosphate, and uniformly mixing; taking 30 mu L of the uniformly mixed solution, spin-coating the solution on a perovskite light absorption layer at the rotating speed of 4000rpm for 30s, and then placing the perovskite light absorption layer in a glass drier for oxidation for 26h to form a hole transport layer;
step f): covering the hole transport layer with a patterned mask plate under an absolute pressure of less than 2 × 10-6And evaporating the metal electrode under the vacuum degree condition of the torr to finish the manufacturing of the perovskite solar cell device.
Further, in the step c), the fullerene derivative is dissolved in a carbon disulfide solvent to prepare a solution with the concentration of 5mg/mL, then 30 μ L of the solution is taken to be spin-coated on the electron transport layer at the rotating speed of 6000rpm, the spin-coating time lasts for 30s, and then annealing treatment is carried out for 10min at 100 ℃ to form an interface modification layer, wherein R is Cl.
Further, the step c) is that the fullerene derivative is dissolved in carbon disulfide solvent to prepare a solution with the concentration of 3mg/mL, then 30 microliter of the solution is taken to be spin-coated on the electron transmission layer at the rotation speed of 4000rpm, the spin-coating time lasts for 30s, and then annealing treatment is carried out for 10min at the temperature of 100 ℃, so as to form an interface modification layer, wherein R is-CH3。
Further, in step f), the metal electrode is a silver electrode.
The invention has the following beneficial effects:
1. the modification of the fullerene derivative is applied to the preparation of the perovskite solar cell, so that the defect is effectively passivated, more effective charge extraction is promoted at the interface, the transmission capability of electrons is stronger, and the short-circuit current and the power conversion efficiency of the device are further improved.
2. The fullerene derivative has high yield and low cost, and can replace the conventional PCBM as a new interface modification material in the preparation of the perovskite solar cell.
Drawings
FIG. 1 is a current-voltage curve for a perovskite solar cell device without modification;
FIG. 2 is a current-voltage curve for a PCBM modified perovskite solar cell device;
FIG. 3 is a current-voltage curve of a fullerene derivative-modified perovskite solar cell device in which the R group is a chlorine atom according to the present invention;
FIG. 4 is a current-voltage curve of a fullerene derivative-modified perovskite solar cell device in which the R group is a methyl group according to the present invention;
FIG. 5 is a test plot of the operational stability of a perovskite solar cell device without modification;
FIG. 6 is a graph showing the operation stability of a fullerene derivative-modified perovskite solar cell device in which the R group is a chlorine atom.
Detailed Description
In order to make the technical solutions of the present invention better understood, the present invention will be further described in detail with reference to the accompanying drawings.
Example 1
The preparation method of the fullerene derivative is characterized by comprising the following steps of:
step 1): sequentially mixing fullerene, cinnamaldehyde,
Figure BDA0002143030480000031
Adding magnesium perchlorate into an o-dichlorobenzene solvent according to the molar ratio of 1:10:10: 4;
step 2): condensing and refluxing for 60min at 180 deg.C to obtain fullerene derivative
Figure BDA0002143030480000032
Step 3): the fullerene derivative was isolated by column chromatography with a yield of 13%.
Wherein R is Cl.
Example 2
The preparation method of the fullerene derivative is characterized by comprising the following steps of:
step 1): sequentially mixing fullerene, cinnamaldehyde,
Figure BDA0002143030480000041
Adding magnesium perchlorate into an o-dichlorobenzene solvent according to the molar ratio of 1:10:10: 4;
step 2): condensing and refluxing for 60min at 180 deg.C to obtain fullerene derivative
Figure BDA0002143030480000042
Step 3): the fullerene derivative was isolated by column chromatography with a yield of 28%.
Wherein R is-CH3。
Example 3
Step a): sequentially and respectively ultrasonically cleaning a patterned ITO conductive glass substrate with the sheet resistance of 15 omega for 10min by using deionized water, ethanol and isopropanol, drying, and irradiating for 10min by using ultraviolet light to remove organic matter micromolecules remained on the surface of the ITO conductive glass;
step b): spin coating 40 μ L TiO 10mg/mL solution at 3000rpm2Spin coating the solution on a conductive glass substrate for 40s, and heat treating at 150 deg.C for 30min to obtain TiO2A thin film layer as an electron transport layer;
step c): by PbI2Preparing perovskite precursor solution with MAI according to the molar ratio of 1: 1; spin-coating 50 mu L of perovskite precursor solution on an electron transport layer at the rotating speed of 6000rpm for 15s, then reducing the rotating speed to 3700rpm, spin-coating 75 mu L of 34.5mg/mL MAI isopropanol solution, maintaining the rotating speed for 45s, and then carrying out annealing treatment at 100 ℃ for 30min to obtain a perovskite thin film as a perovskite light absorption layer;
step d): weighing 80mg of Spiro-OMeTAD, dissolving in 1mL of chlorobenzene, fully dissolving, adding 17.5 mu L of Li-TFSI acetonitrile solution of 520mg/mL and 28.5 mu L of tributyl phosphate, and uniformly mixing; taking 30 mu L of the uniformly mixed solution, spin-coating the solution on a perovskite light absorption layer at the rotating speed of 4000rpm for 30s, and then placing the perovskite light absorption layer in a glass drier for oxidation for 26h to form a hole transport layer;
step e): covering the hole transport layer with a patterned mask plate under an absolute pressure of less than 2 × 10-6And evaporating the metal electrode under the vacuum degree condition of the torr so as to finish the preparation of the perovskite solar cell device.
Example 4
Step a): sequentially and respectively ultrasonically cleaning a patterned ITO conductive glass substrate with the sheet resistance of 15 omega for 10min by using deionized water, ethanol and isopropanol, drying, and irradiating for 10min by using ultraviolet light to remove organic matter micromolecules remained on the surface of the ITO conductive glass;
step b): spin coating 40 μ L TiO 10mg/mL solution at 3000rpm2Spin coating the solution on a conductive glass substrate for 40s, and heat treating at 150 deg.C for 30min to obtain TiO2A thin film layer as an electron transport layer;
step c): dissolving the PCBM fullerene derivative in a chlorobenzene solvent to prepare a solution with the concentration of 15mg/mL, then taking 30 microliter to spin-coat on the electron transport layer at the rotating speed of 1000rpm for 30s, and then annealing at 100 ℃ for 10min to form an interface modification layer;
step d): by PbI2Preparing perovskite precursor solution with MAI according to the molar ratio of 1: 1; spin-coating 50 mu L of perovskite precursor solution on the interface modification layer at the rotating speed of 6000rpm for 15s, then reducing the rotating speed to 3700rpm, spin-coating 75 mu L and 34.5mg/mL of MAI isopropanol solution, maintaining the rotating speed for 45s, and then carrying out annealing treatment at 100 ℃ for 30min to obtain a perovskite thin film as a perovskite light absorption layer;
step e): weighing 80mg of Spiro-OMeTAD, dissolving in 1mL of chlorobenzene, fully dissolving, adding 17.5 mu L of Li-TFSI acetonitrile solution of 520mg/mL and 28.5 mu L of tributyl phosphate, and uniformly mixing; taking 30 mu L of the uniformly mixed solution, spin-coating the solution on a perovskite light absorption layer at the rotating speed of 4000rpm for 30s, and then placing the perovskite light absorption layer in a glass drier for oxidation for 26h to form a hole transport layer;
step f): covering the hole transport layer with a patterned mask plate under an absolute pressure of less than 2 × 10-6And evaporating the metal electrode under the vacuum degree condition of the torr to finish the manufacturing of the perovskite solar cell device.
Example 5
Step a): sequentially and respectively ultrasonically cleaning a patterned ITO conductive glass substrate with the sheet resistance of 15 omega for 10min by using deionized water, ethanol and isopropanol, drying, and irradiating for 10min by using ultraviolet light to remove organic matter micromolecules remained on the surface of the ITO conductive glass;
step b): spin coating 40 μ L TiO 10mg/mL solution at 3000rpm2Spin coating the solution on a conductive glass substrate for 40s, and heat treating at 150 deg.C for 30min to obtain TiO2A thin film layer as an electron transport layer;
step c): dissolving the fullerene derivative obtained in the embodiment 1 in a carbon disulfide solvent to prepare a solution with the concentration of 5mg/mL, then taking 30 microliter to spin-coat on the electron transport layer at the rotating speed of 6000rpm, wherein the spin-coating time lasts for 30s, and then carrying out annealing treatment at 100 ℃ for 10min to form an interface modification layer;
step d): by PbI2Preparing perovskite precursor solution with MAI according to the molar ratio of 1: 1; spin-coating 50 mu L of perovskite precursor solution on the interface modification layer at the rotating speed of 6000rpm for 15s, then reducing the rotating speed to 3700rpm, spin-coating 75 mu L and 34.5mg/mL of MAI isopropanol solution, maintaining the rotating speed for 45s, and then carrying out annealing treatment at 100 ℃ for 30min to obtain a perovskite thin film as a perovskite light absorption layer;
step e): weighing 80mg of Spiro-OMeTAD, dissolving in 1mL of chlorobenzene, fully dissolving, adding 17.5 mu L of Li-TFSI acetonitrile solution of 520mg/mL and 28.5 mu L of tributyl phosphate, and uniformly mixing; taking 30 mu L of the uniformly mixed solution, spin-coating the solution on a perovskite light absorption layer at the rotating speed of 4000rpm for 30s, and then placing the perovskite light absorption layer in a glass drier for oxidation for 26h to form a hole transport layer;
step f): covering the hole transport layer with a patterned mask plate under an absolute pressure of less than 2 × 10-6And evaporating the metal electrode under the vacuum degree condition of the torr to finish the manufacturing of the perovskite solar cell device.
Example 6
Step a): sequentially and respectively ultrasonically cleaning a patterned ITO conductive glass substrate with the sheet resistance of 15 omega for 10min by using deionized water, ethanol and isopropanol, drying, and irradiating for 10min by using ultraviolet light to remove organic matter micromolecules remained on the surface of the ITO conductive glass;
step b): at 3000rpmSpin coating 40 μ L TiO 10mg/mL solution at a concentration of2Spin coating the solution on a conductive glass substrate for 40s, and heat treating at 150 deg.C for 30min to obtain TiO2A thin film layer as an electron transport layer;
step c): dissolving the fullerene derivative obtained in the embodiment 2 in a carbon disulfide solvent to prepare a solution with the concentration of 3mg/mL, then taking 30 microliter to spin-coat on the electron transport layer at the rotation speed of 4000rpm for 30s, and then carrying out annealing treatment at 100 ℃ for 10min to form an interface modification layer;
step d): by PbI2Preparing perovskite precursor solution with MAI according to the molar ratio of 1: 1; spin-coating 50 mu L of perovskite precursor solution on the interface modification layer at the rotating speed of 6000rpm for 15s, then reducing the rotating speed to 3700rpm, spin-coating 75 mu L and 34.5mg/mL of MAI isopropanol solution, maintaining the rotating speed for 45s, and then carrying out annealing treatment at 100 ℃ for 30min to obtain a perovskite thin film as a perovskite light absorption layer;
step e): weighing 80mg of Spiro-OMeTAD, dissolving in 1mL of chlorobenzene, fully dissolving, adding 17.5 mu L of Li-TFSI acetonitrile solution of 520mg/mL and 28.5 mu L of tributyl phosphate, and uniformly mixing; taking 30 mu L of the uniformly mixed solution, spin-coating the solution on a perovskite light absorption layer at the rotating speed of 4000rpm for 30s, and then placing the perovskite light absorption layer in a glass drier for oxidation for 26h to form a hole transport layer;
step f): covering the hole transport layer with a patterned mask plate under an absolute pressure of less than 2 × 10-6And evaporating the metal electrode under the vacuum degree condition of the torr to finish the manufacturing of the perovskite solar cell device.
Examples 1 to 6 will be described below.
Examples 1 and 2 are processes for preparing the fullerene derivative, and the corresponding chemical reaction equations are as follows:
Figure BDA0002143030480000071
wherein R is Cl or-CH3。
The yields of the two prepared fullerene derivatives are respectively 13% and 28%, while the yield of the common fullerene derivative PCBM is only 8.26%, so that the yield of the fullerene derivative is greatly improved compared with the yield of the common PCBM, and the production cost of the fullerene derivative is lower than that of the PCBM.
Fig. 1-4 are J-V curves (current-voltage curves) for the perovskite solar cell devices fabricated in examples 3-6, respectively, from which the Power Conversion Efficiency (PCE) profiles for these four devices can be seen.
The PCE (power conversion efficiency) of the perovskite solar cell device fabricated in example 5 can reach 19% in reverse scan (reverse scan direction), which is significantly higher than the perovskite solar cell devices of example 3 (17.6%) and example 4 (18.3%). Compared to the perovskite solar cell device fabricated in example 3, the perovskite solar cell device of example 5 has almost the same Jsc (short circuit current) magnitude, while FF (fill factor) and Voc (open circuit voltage) are larger. The hysteresis effect of example 5 was 11% which is comparable to example 4 (7%) but significantly reduced from that of example 3 (46%).
The perovskite solar cell device prepared in example 6 can reach a power conversion efficiency of 18.8% in the reverse scan direction, which is somewhat higher than that of example 4 (18.3%), but significantly higher than that of example 3 (17.6%). Compared to the perovskite solar cell device fabricated in example 3, the perovskite solar cell device of example 6 has a larger Jsc (short circuit current), FF (fill factor) and Voc (open circuit voltage). The hysteresis effect of the device made in example 6 was 22% greater than that of example 4 (7%), but significantly reduced from that of example 3 (46%).
The addition of the fullerene derivative layer can effectively improve FF (fill factor) and Voc (open circuit voltage), and further improve the photovoltaic performance of the device.
The steady state PL test data is shown in Table 1 by the formula Te＝A1Τ1+A2Τ2+A1Τ3Calculating to obtain gammaeIn the formula < CHEM > T1、Τ2、Τ3It is meant that three decay times are present,A1、A2、A3is the proportion thereof. From decay time TeIt can be seen that the devices made in examples 5 and 6 have a decay time t e significantly less than the devices made in examples 3 and 4, with the unmodified device made in example 3 having the longest decay time.
The above shows that the modification of the fullerene derivative effectively passivates defects and promotes more effective charge extraction at the interface, and compared with the conventional PCBM, the fullerene derivative provided by the invention has more effective charge extraction, so that the electron transmission capability is stronger, and the short-circuit current and the power conversion efficiency of the device are improved. The fullerene derivative has the advantages that the interface passivation can reduce the defects of the interface, increase the grain size and reduce the non-radiative recombination loss of the interface, so that the open-circuit voltage, the filling factor and the power conversion efficiency of the device are improved.
TABLE 1 Steady-State PL test data
Figure BDA0002143030480000081
Fig. 5 and fig. 6 are operation stability tests of the devices fabricated in examples 3 and 5, and it can be seen that the device fabricated in example 5 can stably output 1000s at a PCE (power conversion efficiency) as high as 18.2%, which is much higher than the output stability of the device fabricated in example 3 (which can only stably output 300s at a lower PCE of 13.1%), thereby illustrating that the device operation stability can be improved after being modified by the fullerene derivative of the present invention compared with an unmodified device.

Claims (6)

1. Use of a fullerene derivative for modifying the interface between an electron transport layer and a perovskite light absorbing layer of a perovskite solar cell, comprising the steps of:
step a): sequentially and respectively ultrasonically cleaning and drying a conductive glass substrate by using deionized water, ethanol and isopropanol, and then irradiating by using ultraviolet light;
step b): manufacturing an electron transmission layer on a conductive glass substrate;
step c): spin-coating the fullerene derivative on the electron transport layer obtained in the step b), and forming an interface modification layer after annealing treatment;
step d): manufacturing a perovskite film on the interface modification layer obtained in the step c) to be used as a perovskite light absorption layer;
step e): manufacturing a hole transport layer on the perovskite light absorption layer;
step f): vacuum evaporating a metal electrode on the hole transport layer to finish the preparation of the perovskite solar cell device;
the structural formula of the fullerene derivative is as follows:
Figure FDA0003016055830000011
wherein R is Cl or-CH3。
2. Use of a fullerene derivative according to claim 1, characterised in that the preparation of the fullerene derivative comprises the steps of:
step 1): sequentially mixing fullerene, cinnamaldehyde,
Figure FDA0003016055830000012
Adding magnesium perchlorate into an o-dichlorobenzene solvent according to the molar ratio of 1:10:10: 4; wherein R is Cl or-CH3；
Step 2): condensing and refluxing at 180 ℃ for 60min to obtain the fullerene derivative of claim 1;
step 3): separating the fullerene derivative by adopting a column chromatography.
3. Use of a fullerene derivative according to claim 1, characterised in that it comprises the steps of:
step a): ultrasonically cleaning a conductive glass substrate with deionized water, ethanol and isopropanol for 10min in sequence, drying, and irradiating with ultraviolet light for 10-15 min;
step b): spin coating 40 μ L TiO 10mg/mL solution at 3000rpm2Spin coating the solution on a conductive glass substrate for 40s, and heat treating at 150 deg.C for 30min to obtain TiO2A thin film layer as an electron transport layer;
step c): dissolving the fullerene derivative in a carbon disulfide solvent to prepare a solution with the concentration of 3mg/mL-5mg/mL, then taking 30 mu L of the solution to spin-coat on the electron transmission layer at the rotating speed of 4000rpm-6000rpm for 30s, and then annealing at 100 ℃ for 10min to form an interface modification layer;
step d): by PbI2Preparing perovskite precursor solution with MAI according to the molar ratio of 1: 1; spin-coating 50 mu L of perovskite precursor solution on the interface modification layer at the rotating speed of 6000rpm for 15s, then reducing the rotating speed to 3700rpm, spin-coating 75 mu L and 34.5mg/mL of MAI isopropanol solution, maintaining the rotating speed for 45s, and then carrying out annealing treatment at 100 ℃ for 30min to obtain a perovskite thin film as a perovskite light absorption layer;
step e): weighing 80mg of Spiro-OMeTAD, dissolving in 1mL of chlorobenzene, fully dissolving, adding 17.5 mu L of Li-TFSI acetonitrile solution of 520mg/mL and 28.5 mu L of tributyl phosphate, and uniformly mixing; taking 30 mu L of the uniformly mixed solution, spin-coating the solution on a perovskite light absorption layer at the rotating speed of 4000rpm for 30s, and then placing the perovskite light absorption layer in a glass drier for oxidation for 26h to form a hole transport layer;
step f): covering the hole transport layer with a patterned mask plate under an absolute pressure of less than 2 × 10-6And evaporating the metal electrode under the vacuum degree condition of the torr so as to finish the preparation of the perovskite solar cell device.
4. The use of a fullerene derivative according to claim 3, wherein the fullerene derivative is dissolved in carbon disulfide solvent to form a solution with a concentration of 5mg/mL, 30 μ L of the solution is spin-coated on the electron transport layer at 6000rpm for 30s, and then the interface modification layer is formed by annealing at 100 ℃ for 10 min.
5. The use of a fullerene derivative according to claim 3, wherein the fullerene derivative is dissolved in carbon disulfide solvent to form a solution with a concentration of 3mg/mL, and then 30 μ L of the solution is spin-coated on the electron transport layer at 4000rpm for 30s, followed by annealing at 100 ℃ for 10min to form the interface modification layer, wherein R is-CH3。
6. Use of a fullerene derivative according to any one of claims 1-5, wherein in step f) the metal electrode is a silver electrode.
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