Highly efficient nickel oxide-based perovskite solar cells based on chlorophyll derivatives and methods of making the same

Abstract

The present application relates to a kind of high-efficiency nickel oxide-based perovskite solar cells based on chlorophyll derivatives, belong to perovskite solar cell technical field.The perovskite solar cell includes transparent conductive glass anode, hole transport layer, chlorophyll derivative passivation layer, perovskite layer, electron transport layer, hole blocking layer and metal cathode from bottom to top in sequence;The hole transport layer is nickel oxide;The chlorophyll derivative passivation layer is the chlorophyll derivative layer containing trifluoroacetate.The perovskite solar cell of the present application is high-efficiency nickel oxide-based perovskite solar cell with chlorophyll derivative containing trifluoroacetate as hole transport layer and perovskite layer interface passivation layer, and photoelectric conversion efficiency can be as high as 25.54%.The preparation method of the perovskite solar cell of the present application, its synthesis process is simple and easy to operate, and has good industrial application prospect with low equipment requirement.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of perovskite solar cells, and particularly relates to a high-efficiency nickel oxide-based perovskite solar cell based on a chlorophyll derivative and a preparation method thereof. BACKGROUND

[0002] Solar energy, as a clean energy, has been widely concerned due to its environmental protection, renewable and wide distribution. The perovskite solar cell is a third-generation solar cell taking a perovskite-type organic metal halide semiconductor material as an absorbing layer, and has the advantages of high conversion rate, low manufacturing cost and easily available material, thus representing an important development direction of solar cell technology and having great application prospect.

[0003] The perovskite solar cell can be divided into a normal structure and an inverted structure, wherein the inverted structure is generally composed of a transparent conductive glass, a hole transport layer, a perovskite absorbing layer, an electron transport layer and a metal counter electrode from top to bottom. Nickel oxide is generally used as the material of the hole transport layer due to its excellent photoelectric performance. However, the nickel oxide also has some defects, such as poor conductivity and redox reaction with the perovskite layer. Therefore, it is urgent and necessary to solve the above problems to obtain a high-efficiency and stable nickel oxide-based perovskite solar cell.

[0004] Chlorophyll and its derivatives are a kind of functional semiconductor materials which are widely present in nature, low in cost and environmentally friendly. The good molecular design can ensure that the molecular energy level and other semiconductor properties can be easily adjusted. In addition, the high energy transfer and electron transfer capacity has been proved. Therefore, if a solar cell based on chlorophyll and its derivatives can be developed, the above problems can be solved, which is the most suitable technical solution. SUMMARY

[0005] The application aims to solve the technical problems in the prior art, and provides a high-efficiency nickel oxide-based perovskite solar cell based on a chlorophyll derivative and a preparation method thereof. The perovskite solar cell of the application is a perovskite solar cell taking a chlorophyll derivative as a passivation layer to modify nickel oxide, and the photoelectric conversion efficiency can be as high as 25.54%.

[0006] In order to solve the above technical problems, the technical scheme of the application is as follows:

[0007] A high-efficiency nickel oxide-based perovskite solar cell based on a chlorophyll derivative 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 structure 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, 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 (bathocuproin), and the metal cathode is Ag.

[0013] In the above technical solution, 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.

[0014] A preparation method of a high-efficiency nickel oxide-based perovskite solar cell based on chlorophyll derivative, comprising the following steps:

[0015] 1) ultraviolet ozone pretreatment of the transparent conductive glass anode;

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

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

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

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

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

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

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

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

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

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

[0026] In the technical scheme, the rotation speed of the spin coating in step 3) is 4000 rpm / min, and the rotation time is 30 s; and the annealing treatment is 100℃ annealing for 10 min.

[0027] The present application has the following beneficial effects:

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

[0029] The preparation method of the perovskite solar cell of the present application has simple and easy synthesis process, low equipment requirement, and good industrial application prospect. BRIEF DESCRIPTION OF DRAWINGS

[0030] The present application will be further described in detail below in combination with the drawings and specific embodiments.

[0031] Figure 1 is the high-efficiency nickel oxide-based perovskite solar cell device structure of the present application with a chlorophyll derivative as a hole transport layer and an interface passivation layer of a perovskite layer.

[0032] Figure 2 is the J-V curve diagram of the high-efficiency nickel oxide-based perovskite solar cell prepared by the embodiment of the present application and the nickel oxide-based perovskite solar cell prepared by the comparative example. DETAILED DESCRIPTION

[0033] In combination Figure 1 The high-efficiency nickel oxide-based perovskite solar cell of the present application based on a chlorophyll derivative includes, 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 structure of the chlorophyll derivative containing trifluoroacetate is as follows:

[0035]

[0036] Preferably, the transparent conductive glass anode is indium tin oxide (ITO), 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 (bathocuproin), 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 preparation method of the high-efficiency nickel oxide-based perovskite solar cell based on a chlorophyll derivative according to the present application comprises the following steps:

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

[0040] The cleaned transparent conductive glass is subjected to ultraviolet ozone pretreatment for 20 minutes;

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

[0042] The transparent conductive glass subjected to ultraviolet ozone pretreatment in step 1) is placed on a spin coater, and nickel oxide nanodispersion liquid is spin-coated at a speed of 2000 rpm / min for 30 seconds. After spin coating, annealing treatment is performed at a temperature of 120°C for 20 minutes.

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

[0044] The device in step 2) is placed in an argon-filled glove box, and a chlorophyll derivative solution containing trifluoroacetate is spin-coated on the hole transport layer. The spin-coating speed is 4000 rpm / min, and the time is 30 seconds. After spin coating, annealing treatment is performed on a hot stage at a temperature 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 the perovskite layer:

[0047] The chlorophyll derivative passivation layer is spin-coated with a perovskite precursor solution, the process is as follows: first, spin-coating at a speed of 1000 rpm / min for 10 seconds, then spin-coating at a speed of 5000 rpm / min for 40 seconds, and 200 microliters of chlorobenzene is added dropwise at the last 5 seconds, and the spin-coating is finished, and then the device is placed on a hot stage for annealing treatment, the annealing temperature and time are 100 DEG C for 30 minutes;

[0048] 5) Preparation of the electron transport layer:

[0049] The electron transport layer is evaporated on the perovskite layer by using a vacuum evaporation coating machine at a pressure less than 6*10 -4 Pa, the evaporation rate is 0.1 A / s.

[0050] 6) Preparation of the hole blocking layer:

[0051] The hole blocking layer is continuously evaporated on the device with the electron transport layer, the evaporation rate is 0.1 A / s.

[0052] 7) Preparation of the metal cathode:

[0053] The metal cathode is continuously evaporated on the device with the hole blocking layer, the evaporation rate is 0.1 A / s.

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

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

[0056] The high-efficiency nickel oxide-based perovskite solar cell of the application, when the perovskite layer is Cs 0.05 FA 0.85 MA 0.1 PbI3, the preparation process of the precursor solution is as follows:

[0057] In an argon glove box, 1.5Mol of PbI2 (760.6mg), 1.4Mol of FAI (239.7mg), CsI (19.5mg), MAI (238mg) and 0.14Mol of MACl (13.3mg) are dissolved in 1mL of DMF / DMSO solution with a volume ratio of 4:1, and stirred at room temperature for 1 hour.

[0058] The preparation process of the nanodispersion of the hole transport layer is as follows:

[0059] In an argon glove box, 10 mg of nano-nickel oxide powder was weighed and transferred to 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 and are not intended to limit 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 isopropyl alcohol 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 air, add 1 mL of ultrapure water, and sonicate in an ultrasonic machine for 5-10 minutes.

[0065] 3) After pre-treating the ITO with UV ozone for 20 minutes, place it on a spin coater and spin-coat the nickel oxide nanodispersion at 2000 rpm / min for 30 seconds. After the spin coating is completed, place it 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 the powder to an argon-filled glove box, 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; placing the substrate into the glove box, and spin-coating the chlorophyll derivative solution on the hole transport layer at a speed of 4000 rpm / min for 30 seconds. After spin coating, the substrate was placed on a hot plate for annealing at 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 0.1PbI3 precursor solution, 1.5Mol of PbI2(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 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, the process was first spin-coated at 1000rpm / min for 10 seconds, and then spin-coated at 5000rpm / min for 40 seconds, and 200 microliters of chlorobenzene was added at the end of 5 seconds, and then placed on the hot stage for annealing treatment, the annealing temperature and time was 100°C for 30 minutes.

[0070] 6) Finally, the substrate was sent to the organic evaporation deposition machine, and when the pressure in the chamber was lower than 6*10 -4 Pa, the electron transport layer C 60 was evaporated at an evaporation rate of 0.1A C 60 , and the film thickness was 20nm; the hole blocking layer BCP was continuously evaporated on the electron transport layer at an evaporation rate of 0.1A , and the BCP film thickness was 6nm; the cathode silver was continuously evaporated on the hole blocking layer at an evaporation rate of 0.1A , and the silver film thickness was 60nm. Thus, a high-efficiency nickel oxide-based perovskite solar cell based on chlorophyll derivative as the interface passivation layer of the hole transport layer and the perovskite layer was obtained. The device structure is shown in Figure 1 . In this example, the thickness of the hole transport layer was 20nm, the thickness of the chlorophyll derivative passivation layer was 2nm, the thickness of the perovskite layer was 500nm, the thickness of the electron transport layer was 20nm, the thickness of the hole blocking layer was 6nm, and the thickness of the metal cathode was 60nm. The thickness of each layer can actually be any value within the aforementioned defined range, and here only the preferred thickness value is given.

[0071] Comparative Example

[0072] 1) The etched ITO was sequentially treated with ITO cleaning agent, deionized water, alcohol, acetone, and isopropanol for 30 minutes under ultrasonic treatment;

[0073] 2) A nickel oxide nanodispersion was prepared, 10mg of nanometer nickel oxide powder was weighed in an argon glove box, transferred to the air, 1mL of ultrapure water was added, and ultrasonic treatment was performed for 5-10 minutes in an ultrasonic machine.

[0074] 3) After ultraviolet ozone pretreatment of the ITO for 20 minutes, the ITO was placed on a spin coater, and the nickel oxide nanodispersion was spin-coated at 2000rpm / min for 30s, and then placed on a hot stage for annealing treatment, the annealing temperature and time was 120°C for 20 minutes.

[0075] 4) Prepare Cs in an argon glove box 0.05 FA 0.85 MA 0.1 For the PbI3 precursor solution, 1.5 mol of PbI2 (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 a 4:1 DMF / DMSO solution and stirred at room temperature for 1 hour. The perovskite precursor solution was spin-coated onto the hole transport layer, initially at 1000 rpm / min for 10 seconds, then at 5000 rpm / min for 40 seconds. Five seconds before the spin-coating, 200 μL of chlorobenzene was added dropwise. After the spin-coating process, the layer was annealed on a hot plate at 100°C 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 silver film thickness is 60 nm. Thus, a nickel oxide-based perovskite solar cell without a passivation layer is obtained. In this comparative example, the hole transport layer thickness is 20 nm, the perovskite layer thickness is 500 nm, the electron transport layer thickness is 20 nm, the hole blocking layer thickness is 6 nm, and the metal cathode thickness is 60 nm.

[0077] Table 1 shows the photovoltaic parameters of a high-efficiency nickel oxide-based perovskite solar cell device prepared in accordance with the present invention, using a chlorophyll derivative as a passivation layer at the interface between the hole transport layer and the perovskite layer, and a passivation-free nickel oxide-based perovskite solar cell prepared in a comparative example. Table 1 shows that the optimal chlorophyll derivative concentration is 1.0 mg / mL, achieving a photoelectric conversion efficiency of 25.54%.

[0078] Table 1

[0079]

[0080]

[0081] Figure 2J-V curve diagram of high-efficiency nickel oxide-based perovskite solar cell prepared by taking chlorophyll derivative as the interface passivation layer of hole transport layer and perovskite layer and the nickel oxide-based perovskite solar cell prepared by the comparative example without passivation layer, and corresponding to Table 1. The high-efficiency nickel oxide-based perovskite solar cell prepared by taking chlorophyll derivative as the interface passivation layer of hole transport layer and perovskite layer has a significant improvement in photoelectric conversion efficiency compared with the nickel oxide-based perovskite solar cell without passivation layer. Meanwhile, under the condition of 1 mg / mL concentration of chlorophyll derivative, the photoelectric conversion efficiency of the perovskite solar cell can reach 25.54%.

[0082] Obviously, the above embodiments are only examples for clearly illustrating the present application, and are not intended to limit the embodiments. Based on the above description, other different forms of changes or variations can be made by those skilled in the art. Here, all the embodiments are not required to be exhausted, and the obvious changes or variations derived therefrom are still within the protection scope of the present application.

Claims

1. A high-efficiency nickel oxide-based perovskite solar cell based on chlorophyll derivatives, comprising, 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; Characterized in that, The hole transport layer is nickel oxide; The chlorophyll derivative passivation layer is a trifluoroacetate-containing chlorophyll derivative layer.

2. The high efficiency nickel oxide based perovskite solar cell according to claim 1, characterized in that, Wherein, The structure of the trifluoroacetate-containing chlorophyll derivative 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), 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 bathocuproin, 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 15-25 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.

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

6. The preparation method according to claim 5, characterized in that Step 3) specifically comprises the following steps: Place the device with the spin-coated hole transport layer in step 2) on a film applicator, spin-coat the trifluoroacetate-containing chlorophyll derivative solution, and after spin-coating, perform annealing treatment.

7. The production method according to claim 6, characterized by, The concentration of the trifluoroacetate-containing chlorophyll derivative solution 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 The spin-coating speed in step 3) is 4000 rpm / min, and the rotation time is 30 s;The annealing treatment is annealing at 100℃ for 10 min.

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