High-efficiency nickel oxide-based perovskite solar cell based on chlorophyll derivative and preparation method of high-efficiency nickel oxide-based perovskite solar cell

Abstract

The invention relates to a chlorophyll derivative-based efficient nickel oxide-based perovskite solar cell, and belongs to the technical field of perovskite solar cells. The perovskite solar cell sequentially comprises a transparent conductive glass anode, a hole transport layer, a chlorophyll derivative passivation layer, a perovskite layer, an electron transport layer, a hole barrier layer and a metal cathode from bottom to top, the hole transport layer is nickel oxide; and the chlorophyll derivative passivation layer is a chlorophyll derivative layer containing trifluoroacetate. The perovskite solar cell is an efficient nickel oxide-based perovskite solar cell with chlorophyll derivatives containing trifluoroacetate as a hole transport layer and a perovskite layer interface passivation layer, and the photoelectric conversion efficiency of the perovskite solar cell can reach 25.54%. According to the preparation method of the perovskite solar cell, the synthesis process is simple and easy to implement, the requirement for equipment is low, and the preparation method has a good industrial application prospect.

Description

Technical Field

[0001] The present invention belongs to the technical field of perovskite solar cells, and in particular relates to a high-efficiency nickel oxide-based perovskite solar cell based on chlorophyll derivatives and a preparation method thereof. Background Art

[0002] As a clean energy, solar energy has attracted widespread attention from the society for its advantages such as environmental protection, renewable and wide distribution. Perovskite solar cells are the third generation of solar cells that use perovskite-type organic metal halide semiconductor materials as light-absorbing layers. They have the advantages of high conversion rate, low manufacturing cost and easy availability of materials. They represent an important development direction of solar cell technology and have great application prospects.

[0003] Perovskite solar cells can be divided into formal and trans structures, where the trans structure is generally composed of five parts from top to bottom: transparent conductive glass, hole transport layer, perovskite absorption layer, electron transport layer, and metal counter electrode. Nickel oxide is generally used as a material for the hole transport layer due to its excellent photoelectric properties. However, nickel oxide also has some disadvantages, such as poor conductivity and redox reaction with the perovskite layer. Therefore, in order to obtain efficient and stable nickel oxide-based perovskite solar cells, it is urgent and necessary to solve the above problems.

[0004] Chlorophyll and its derivatives are a class of functional semiconductor materials that are widely found in nature, are low-cost and environmentally friendly. Good molecular design can ensure that its semiconductor properties such as molecular energy levels can be easily adjusted. In addition, its high energy transfer and electron transfer capabilities have long been proven. Therefore, if the above problems can be solved at the same time by developing solar cells based on chlorophyll and its derivatives, it will be the most suitable technical solution. Summary of the invention

[0005] The present invention aims to solve the technical problems in the prior art and provide a high-efficiency nickel oxide-based perovskite solar cell based on chlorophyll derivatives and a preparation method thereof. The perovskite solar cell of the present invention is a perovskite solar cell in which nickel oxide is modified using a chlorophyll derivative as a passivation layer, and its photoelectric conversion efficiency can be as high as 25.54%.

[0006] In order to solve the above technical problems, the technical solutions of the present invention are as follows:

[0007] A high-efficiency nickel oxide-based perovskite solar cell based on chlorophyll derivatives, which comprises, from bottom to top, a transparent conductive glass anode, a hole transport layer, a chlorophyll derivative passivation layer, a perovskite layer, an electron transport layer, a hole blocking layer and a metal cathode;

[0008] The hole transport layer is nickel oxide;

[0009] The chlorophyll derivative passivation layer is a chlorophyll derivative layer containing trifluoroacetate.

[0010] In the above technical solution, the structural formula of the chlorophyll derivative containing trifluoroacetate is as follows:

[0011]

[0012] In the above technical solution, the transparent conductive glass anode is indium tin oxide ITO, and the perovskite layer is Cs 0.05 FA 0.85 MA 0.1 PbI 3 , the electron transport layer is C 60 (fullerene), the hole blocking layer is BCP (bathocuproine), and the metal cathode is Ag.

[0013] In the above technical solution, the thickness of the hole transport layer is 15-25nm, the thickness of the chlorophyll derivative passivation layer is 1-2nm, the thickness of the perovskite layer is 500-600nm, the thickness of the electron transport layer is 20-25nm, the thickness of the hole blocking layer is 5-6nm, and the thickness of the metal cathode is 50-70nm.

[0014] A method for preparing a high-efficiency nickel oxide-based perovskite solar cell based on chlorophyll derivatives comprises the following steps:

[0015] 1) Pre-treating the transparent conductive glass anode with ultraviolet ozone;

[0016] 2) Spin coating a hole transport layer on the transparent conductive glass;

[0017] 3) spin coating a chlorophyll derivative passivation layer on the hole transport layer;

[0018] 4) spin coating a perovskite layer on the chlorophyll derivative passivation layer;

[0019] 5) evaporating an electron transport layer on the perovskite layer;

[0020] 6) evaporating a hole blocking layer on the electron transport layer;

[0021] 7) Evaporating a metal cathode on the hole blocking layer.

[0022] In the above technical solution, step 3) specifically includes the following steps:

[0023] The device on which the hole transport layer is spin-coated in step 2) is placed on a spin coater, and a chlorophyll derivative solution containing trifluoroacetate is spin-coated. After the spin coating is completed, an annealing treatment is performed.

[0024] In the above technical solution, the concentration of the chlorophyll derivative solution containing trifluoroacetate is 0.5-2.0 mg / mL.

[0025] In the above technical solution, the concentration of the chlorophyll derivative solution containing trifluoroacetate is 1.0 mg / mL.

[0026] In the above technical solution, in step 3), the spin coating speed is 4000 rpm / min and the rotation is 30 seconds; the annealing treatment is annealing at 100° C. for 10 minutes.

[0027] The beneficial effects of the present invention are:

[0028] The perovskite solar cell of the present invention is a high-efficiency nickel oxide-based perovskite solar cell using a chlorophyll derivative containing trifluoroacetate as a hole transport layer and a perovskite layer interface passivation layer, and its photoelectric conversion efficiency can be as high as 25.54%.

[0029] The preparation method of the perovskite solar cell of the present invention has a simple and easy synthesis process, low requirements on equipment, and has good industrial application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] The present invention is further described in detail below in conjunction with the accompanying drawings and specific embodiments.

[0031] Figure 1 This is a structural diagram of a high-efficiency nickel oxide-based perovskite solar cell device of the present invention, which uses a chlorophyll derivative as a hole transport layer and a perovskite layer interface passivation layer.

[0032] Figure 2 It is a JV curve diagram of a high-efficiency nickel oxide-based perovskite solar cell device prepared in an embodiment of the present invention using a chlorophyll derivative as a hole transport layer and a perovskite layer interface passivation layer and a nickel oxide-based perovskite solar cell device prepared in a comparative example. DETAILED DESCRIPTION

[0033] Combination Figure 1 The high-efficiency nickel oxide-based perovskite solar cell based on chlorophyll derivatives of the present invention comprises, from bottom to top, a transparent conductive glass anode, a hole transport layer, a chlorophyll derivative passivation layer, a perovskite layer, an electron transport layer, a hole blocking layer and a metal cathode; wherein the hole transport layer is nickel oxide, and the chlorophyll derivative passivation layer is a chlorophyll derivative layer containing trifluoroacetate.

[0034] Preferably, the structural formula of the chlorophyll derivative containing trifluoroacetate is as follows:

[0035]

[0036] Preferably, the transparent conductive glass anode is indium tin oxide ITO, and the perovskite layer is Cs 0.05 FA 0.85 MA 0.1 PbI 3 , the electron transport layer is C 60 (fullerene), the hole blocking layer is BCP (bathocuproine), and the metal cathode is Ag.

[0037] Preferably, the thickness of the hole transport layer is 15-25 nm, the thickness of the chlorophyll derivative passivation layer is 1-2 nm, the thickness of the perovskite layer is 500-600 nm, the thickness of the electron transport layer is 20-25 nm, the thickness of the hole blocking layer is 5-6 nm, and the thickness of the metal cathode is 50-70 nm.

[0038] The method for preparing a high-efficiency nickel oxide-based perovskite solar cell based on chlorophyll derivatives of the present invention comprises the following steps:

[0039] 1) Treatment of transparent conductive glass anode:

[0040] The cleaned transparent conductive glass was subjected to UV-ozone pretreatment for 20 minutes;

[0041] 2) Preparation and treatment of hole transport layer:

[0042] The transparent conductive glass pretreated with UV ozone in step 1) is placed on a coating machine, and the nickel oxide nano-dispersion liquid is spin-coated at a speed of 2000 rpm / min for 30 seconds. After the spin coating is completed, an annealing treatment is performed at a temperature and time of 120° C. for 20 minutes;

[0043] 3) Preparation and treatment of chlorophyll derivative passivation layer:

[0044] The device in step 2) is placed in a glove box filled with argon gas, and a chlorophyll derivative solution containing trifluoroacetate is spin-coated on the hole transport layer at a spin-coating speed of 4000 rpm / min for 30 seconds. After the spin-coating is completed, the device is placed on a hot stage for annealing at a temperature and time of 100° C. for 10 minutes;

[0045] Preferably, the concentration of the chlorophyll derivative solution containing trifluoroacetate is 0.5-2 mg / mL, and most preferably, the concentration of the chlorophyll derivative solution containing trifluoroacetate is 1 mg / mL.

[0046] 4) Preparation of perovskite layer:

[0047] The perovskite precursor solution was spin-coated on the chlorophyll derivative passivation layer, and the process was as follows: first, the spin-coating speed was 1000 rpm / min, the time was 10 seconds, and then the spin-coating speed was 5000 rpm / min, the time was 40 seconds, and 200 microliters of chlorobenzene was added dropwise 5 seconds before the end of the spin coating. After the spin coating was completed, it was placed on a hot stage for annealing, and the annealing temperature and time were 100° C. for 30 minutes;

[0048] 5) Preparation of electron transport layer:

[0049] Using vacuum evaporation coating machine at a pressure less than 6*10 -4 Pa, the electron transport layer is evaporated on the perovskite layer, and its evaporation rate is

[0050] 6) Preparation of hole barrier layer:

[0051] The hole blocking layer is continuously evaporated on the device with the evaporated electron transport layer, and its evaporation rate is

[0052] 7) Preparation of metal cathode:

[0053] The metal cathode is further evaporated on the device with the hole-blocking layer, and the evaporation rate is

[0054] The preparation process of the chlorophyll derivative solution containing trifluoroacetate used in the present invention is as follows:

[0055] 10 mg, 20 mg, 15 mg, and 5 mg of chlorophyll derivative powder were weighed in air, respectively, and transferred to a glove box filled with argon. 10 mL of DMSO solution was added, and stirred at room temperature for 5 minutes to obtain chlorophyll derivative solutions containing trifluoroacetate of different concentrations.

[0056] The high-efficiency nickel oxide-based perovskite solar cell of the present invention, when the perovskite layer is Cs 0.05 FA 0.85 MA 0.1 PbI 3 When the precursor solution is prepared, the process is as follows:

[0057] In an argon glove box, 1.5 mol of PbI 2 (760.6 mg), 1.4 Mol of FAI (239.7 mg), CsI (19.5 mg), MAI (238 mg) and 0.14 Mol of MACl (13.3 mg) were dissolved in 1 mL of DMF / DMSO solution with a volume ratio of 4:1 and stirred at room temperature for 1 hour.

[0058] The hole transport layer is nickel oxide, and the preparation process of its nano-dispersion liquid is as follows:

[0059] In an argon glove box, 10 mg of nano nickel oxide powder was weighed, transferred to the air, 1 mL of ultrapure water was added, and ultrasonicated in an ultrasonic machine for 5-10 minutes to obtain a 10 mg / mL nickel oxide nano dispersion.

[0060] In order to have a deeper understanding of the present invention, the technical solution is clearly and completely described below in conjunction with the embodiments. However, the embodiments of the present invention are only for explaining the present invention rather than limiting the present invention. All other implementation cases obtained by those skilled in the art without making any creative work are within the scope of protection of the present invention.

[0061] The raw materials used in the following examples are all commercially available products.

[0062] Example

[0063] 1) The etched ITO was ultrasonically treated with ITO cleaning agent, deionized water, alcohol, acetone, and isopropanol for 30 minutes in sequence;

[0064] 2) Prepare nickel oxide nano-dispersion: in an argon glove box, weigh 10 mg of nano nickel oxide powder, transfer it to the air, add 1 mL of ultrapure water, and sonicate it in an ultrasonic machine for 5-10 minutes.

[0065] 3) After the ITO is pretreated with UV ozone for 20 minutes, it is placed on a coater and spin-coated with a nickel oxide nano-dispersion at 2000 rpm / min for 30 seconds. After the spin coating is completed, it is placed on a hot plate for annealing at 120° C. for 20 minutes.

[0066] 4) preparing a chlorophyll derivative solution containing trifluoroacetate, weighing 10 mg, 20 mg, 15 mg, and 5 mg of chlorophyll derivative powder in air, respectively, transferring them to a glove box filled with argon, adding 10 mL of DMSO solution, respectively, to prepare chlorophyll derivative solutions with concentrations of 1.0, 2.0, 1.5, and 0.5 mg / mL, and stirring at room temperature for 5 minutes; sending the substrate into the glove box, spin coating the chlorophyll derivative solution on the hole transport layer at a speed of 4000 rpm / min for 30 seconds, and placing it on a hot stage for annealing after the spin coating is completed, and the annealing temperature and time are 100° C. for 10 minutes.

[0067] Among them, the structural formula of the chlorophyll derivative containing trifluoroacetate is as follows:

[0068]

[0069] 5) Prepare Cs in an argon glove box 0.05 FA 0.85 MA 0.1 PbI3 Precursor solution, 1.5Mol PbI 2 (760.6mg), 1.4Mol of FAI (239.7mg), CsI (19.5mg), MAI (238mg) and 0.14Mol of MACl (13.3mg) were dissolved in 1mL of DMF / DMSO solution with a volume ratio of 4:1 and stirred at room temperature for 1 hour. The perovskite precursor solution was spin-coated on the chlorophyll derivative passivation layer, and the process was firstly spin-coated at a speed of 1000rpm / min for 10 seconds, then at a speed of 5000rpm / min for 40 seconds, and 200 microliters of chlorobenzene was added 5 seconds before the end. After the spin coating was completed, it was placed on a hot stage for annealing, and the annealing temperature and time were 100℃ for 30 minutes.

[0070] 6) Finally, the substrate is sent into the organic evaporation deposition machine. When the pressure in the chamber is lower than 6*10 -4 Pa evaporation electron transport layer C 60 , its evaporation rate C 60 The film thickness is 20nm; the hole blocking layer BCP is continuously evaporated on the electron transport layer, and its evaporation rate is The BCP film thickness is 6nm; cathode silver is continuously evaporated on the hole barrier layer, and its evaporation rate is The silver film thickness is 60nm. Thus, a highly efficient nickel oxide-based perovskite solar cell based on chlorophyll derivatives as the hole transport layer and the interface passivation layer of the perovskite layer is obtained. The device structure is shown in FIG. Figure 1 As shown. In this embodiment, the thickness of the hole transport layer is 20nm, the thickness of the chlorophyll derivative passivation layer is 2nm, the thickness of the perovskite layer is 500nm, the thickness of the electron transport layer is 20nm, the thickness of the hole blocking layer is 6nm, and the thickness of the metal cathode is 60nm. The thickness of each layer can actually be any value within the aforementioned limited range, and only the preferred thickness values ​​are given here.

[0071] Comparative Example

[0072] 1) The etched ITO was ultrasonically treated with ITO cleaning agent, deionized water, alcohol, acetone, and isopropanol for 30 minutes in sequence;

[0073] 2) Prepare nickel oxide nano-dispersion: in an argon glove box, weigh 10 mg of nano nickel oxide powder, transfer it to the air, add 1 mL of ultrapure water, and sonicate it in an ultrasonic machine for 5-10 minutes.

[0074] 3) After the ITO is pretreated with UV ozone for 20 minutes, it is placed on a coater and spin-coated with a nickel oxide nano-dispersion at 2000 rpm / min for 30 seconds. After the spin coating is completed, it is placed on a hot plate for annealing at 120° C. for 20 minutes.

[0075] 4) Prepare Cs in an argon glove box 0.05 FA 0.85 MA 0.1 PbI 3 Precursor solution, 1.5Mol PbI 2 (760.6mg), 1.4Mol of FAI (239.7mg), CsI (19.5mg), MAI (238mg) and 0.14Mol of MACl (13.3mg) were dissolved in 1mL of DMF / DMSO solution with a volume ratio of 4:1 and stirred at room temperature for 1 hour. The perovskite precursor solution was spin-coated on the hole transport layer, and the process was firstly spin-coated at a speed of 1000rpm / min for 10 seconds, then at a speed of 5000rpm / min for 40 seconds, and 200 microliters of chlorobenzene was added 5 seconds before the end. After the spin coating was completed, it was placed on a hot stage for annealing, and the annealing temperature and time were 100℃ for 30 minutes.

[0076] 5) Finally, the substrate is sent into the organic evaporation deposition machine. When the pressure in the chamber is lower than 6*10 -4 Pa evaporation electron transport layer C 60 , its evaporation rate C 60 The film thickness is 20nm; the hole blocking layer BCP is continuously evaporated on the electron transport layer, and its evaporation rate is The BCP film thickness is 6nm; cathode silver is continuously evaporated on the hole barrier layer, and its evaporation rate is The thickness of the silver film is 60 nm. Thus, a nickel oxide-based perovskite solar cell without a passivation layer is obtained. In this comparative example, the thickness of the hole transport layer is 20 nm, the thickness of the perovskite layer is 500 nm, the thickness of the electron transport layer is 20 nm, the thickness of the hole blocking layer is 6 nm, and the thickness of the metal cathode is 60 nm.

[0077] Table 1 shows the photovoltaic parameters of the high-efficiency nickel oxide-based perovskite solar cell device based on chlorophyll derivatives as the interface passivation layer between the hole transport layer and the perovskite layer prepared in the embodiment of the present invention and the nickel oxide-based perovskite solar cell without passivation layer prepared in the comparative example. It can be seen from Table 1 that the most suitable concentration of chlorophyll derivatives is 1.0 mg / mL, under which the photoelectric conversion efficiency of the device is as high as 25.54%.

[0078] Table 1

[0079]

[0080]

[0081] Figure 2 It is a JV curve diagram of a high-efficiency nickel oxide-based perovskite solar cell with a chlorophyll derivative as a hole transport layer and a perovskite layer interface passivation layer prepared in an embodiment of the present invention and a nickel oxide-based perovskite solar cell device without a passivation layer prepared in a comparative example, and corresponds to Table 1. The high-efficiency nickel oxide-based perovskite solar cell based on chlorophyll derivatives as a hole transport layer and a perovskite layer interface passivation layer prepared in the present invention has a significant improvement in photoelectric conversion efficiency compared to a nickel oxide perovskite solar cell without a passivation layer. At the same time, under the condition of a chlorophyll derivative concentration of 1 mg / mL, the photoelectric conversion efficiency of the perovskite solar cell can reach 25.54%.

[0082] Obviously, the above embodiments are merely examples for the purpose of clear explanation, and are not intended to limit the implementation methods. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation methods here. The obvious changes or modifications derived therefrom are still within the scope of protection of the invention.

Claims

1. A high-efficiency nickel oxide-based perovskite solar cell based on chlorophyll derivatives, which comprises, from bottom to top, a transparent conductive glass anode, a hole transport layer, a chlorophyll derivative passivation layer, a perovskite layer, an electron transport layer, a hole blocking layer and a metal cathode; It is characterized in that The hole transport layer is nickel oxide; The chlorophyll derivative passivation layer is a chlorophyll derivative layer containing trifluoroacetate.

2. The high-efficiency nickel oxide-based perovskite solar cell according to claim 1, characterized in that: in, The structural formula of chlorophyll derivatives containing trifluoroacetate is as follows:

3. The high-efficiency nickel oxide-based perovskite solar cell according to claim 1, characterized in that: The transparent conductive glass anode is indium tin oxide ITO, and the perovskite layer is Cs 0.05 FA 0.85 MA 0.1 PbI3, the electron transport layer is C 60 (fullerene), the hole blocking layer is BCP (bathocuproine), and the metal cathode is Ag.

4. The high-efficiency nickel oxide-based perovskite solar cell according to claim 1, characterized in that: The thickness of the hole transport layer is 15-25nm, the thickness of the chlorophyll derivative passivation layer is 1-2nm, the thickness of the perovskite layer is 500-600nm, the thickness of the electron transport layer is 20-25nm, the thickness of the hole blocking layer is 5-6nm, and the thickness of the metal cathode is 50-70nm.

5. A method for preparing a high-efficiency nickel oxide-based perovskite solar cell according to any one of claims 1 to 4, characterized in that: The following steps are involved: 1) Pre-treating the transparent conductive glass anode with ultraviolet ozone; 2) Spin coating a hole transport layer on the transparent conductive glass; 3) spin coating a chlorophyll derivative passivation layer on the hole transport layer; 4) spin coating a perovskite layer on the chlorophyll derivative passivation layer; 5) evaporating an electron transport layer on the perovskite layer; 6) evaporating a hole blocking layer on the electron transport layer; 7) Evaporating a metal cathode on the hole blocking layer.

6. The preparation method according to claim 5, characterized in that: Step 3) specifically includes the following steps: The device on which the hole transport layer is spin-coated in step 2) is placed on a spin coater, and a chlorophyll derivative solution containing trifluoroacetate is spin-coated. After the spin coating is completed, an annealing treatment is performed.

7. The preparation method according to claim 6, characterized in that: The concentration of the chlorophyll derivative solution containing trifluoroacetate is 0.5-2.0 mg / mL.

8. The preparation method according to claim 6, characterized in that: The concentration of the trifluoroacetate-containing chlorophyll derivative solution is 1.0 mg / mL.

9. The preparation method according to claim 6, characterized in that: In step 3), the spin coating speed is 4000 rpm / min and the rotation is 30 seconds; the annealing treatment is annealing at 100° C. for 10 minutes.

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