CN-121974916-A - Imide metal naphthalocyanine derivative and preparation and photovoltaic application thereof

Abstract

An imide metal naphthalocyanine derivative, a preparation method and a photovoltaic application thereof belong to the field of perovskite solar energy photovoltaic. The metal naphthalocyanine derivative forms a larger pi-conjugated system, and the pi-conjugated expansion can enhance pi-pi interaction between molecules, so that the charge transfer capability is improved. According to the lewis acid-base theory, molecules containing nitrogen, oxygen, etc. as electron donating atoms can act as passivating agents to reduce defects in the perovskite. According to the invention, the imide group with multiple coordination sites is introduced into the periphery of naphthalocyanine, and the obtained derivative is added into the perovskite film as a passivating agent in a bulk phase doping mode, so that not only can the non-coordination ions (such as Pb 2+ ) be passivated efficiently, but also the perovskite crystallization process can be regulated and controlled. Finally, the method is favorable for forming the perovskite active layer with better crystallinity, larger grain size and more uniform morphology, and higher photoelectric conversion efficiency is obtained.

Inventors

• YU ZE
• LI JUNPENG

Assignees

• 大连理工大学

Dates

Publication Date

20260505

Application Date

20260127

Claims (9)

1. 1. The imide metal naphthalocyanine derivative is characterized by having a structural general formula shown in the following formula I: ; wherein R is selected from the group consisting of linear alkyl, branched alkyl, linear alkoxy, branched alkoxy, linear alkylthio, branched alkylthio, alkenyl, and aryl; m is a metal selected from nickel, copper, zinc, cobalt, palladium, platinum, iron, magnesium, lead, tin, vanadium, manganese, calcium, barium or strontium.
2. 2. The naphthalocyanine derivative of imide metal in claim 1, wherein R is a linear alkyl or branched alkyl, M is a metal selected from nickel, copper, zinc, cobalt, palladium, platinum, iron, magnesium, lead, tin, vanadium, manganese, calcium, barium or strontium.
3. 3. The imide metal naphthalocyanine derivative according to claim 2, wherein the structural general formula of the imide metal naphthalocyanine derivative is shown as the following formula II: ; in the formula II, n is 0-30, M is metal, and the metal is selected from nickel, copper, zinc, cobalt, palladium, platinum, iron, magnesium, lead, tin, vanadium, manganese, calcium, barium or strontium.
4. 4. An imide metal naphthalocyanine derivative according to claim 3, characterized in that M is selected from nickel, zinc, copper, iron.
5. 5. The use of an imide metal naphthalocyanine derivative according to any of claims 1-4, characterized in that the imide metal naphthalocyanine derivative is applied in perovskite solar cells.
6. 6. A perovskite solar cell, characterized in that the cell comprises the imide metal naphthalocyanine derivative according to any one of claims 1 to 4.
7. 7. The perovskite solar cell according to claim 6, wherein the perovskite solar cell structure is a planar formal structure, and comprises a transparent conductive substrate, an electron transport layer, a perovskite light absorption layer, a hole transport layer and a metal electrode from bottom to top.
8. 8. A perovskite solar cell according to claim 7, wherein the imide metal naphthalocyanine derivative is applied as a bulk passivating agent to perovskite solar cells.
9. 9. The method for manufacturing a perovskite solar cell according to any one of claims 6 to 8, comprising the steps of ultrasonically cleaning a conductive glass substrate with a solvent, manufacturing an electron transport layer on the cleaned conductive glass substrate by a chemical bath deposition method or a thermosol spray method, manufacturing a perovskite layer on the electron transport layer by a one-step antisolvent method, spin-coating a hole transport layer on a perovskite thin film, and vacuum-evaporating gold/silver electrodes.

Description

Imide metal naphthalocyanine derivative and preparation and photovoltaic application thereof Technical Field The invention belongs to the technical field of perovskite photovoltaics, and particularly relates to an imide metal naphthalocyanine derivative, a preparation method thereof and a photovoltaic application thereof. Background With the continuous development of society, the energy demand of human beings is also increasing. The traditional fossil energy is not renewable and the reserves are continuously reduced, and the exploitation difficulty is gradually increased, so people are increasingly concerned about and develop clean and renewable energy sources such as solar energy, wind energy, water energy, geothermal energy and the like. Among the many emerging photovoltaic technologies, perovskite solar cells among the third generation solar cells are attracting attention by virtue of their excellent physicochemical properties of strong light absorption capacity, long carrier diffusion length, high defect tolerance, high solution processability, and the like. Since 2009, perovskite solar cells have now demonstrated efficiencies comparable to crystalline silicon solar cells, with considerable development prospects. The current common method for preparing perovskite layers in laboratories is solution spin coating. However, this process causes the perovskite precursor solution to instantaneously reach extremely high supersaturation due to rapid removal of solvent during spin-coating anti-solvent and annealing, thereby inducing rapid, disordered nucleation and growth of crystals. This rapid crystallization is prone to forming polycrystalline films composed of a large number of nano-to micron-sized grains. In polycrystalline thin films, grain boundaries are interfacial regions between adjacent grains of the same chemical composition and different crystal orientations. The atomic arrangement at the grain boundaries is disordered, the chemical bonds are broken or unsaturated, and thus becomes an enriched region of defects (especially uncoordinated Pb 2+ and I -). The smaller the grain size, the larger the total area of grain boundaries and the higher the defect density. These defects can limit charge transport, induce ion mobility and hysteresis, and exacerbate non-radiative recombination of carriers, thereby affecting the photovoltaic performance of the cell. Disclosure of Invention In order to solve the problems, the invention provides an imide metal naphthalocyanine derivative which is used as a bulk phase passivating agent in perovskite solar cell devices. Specifically, the derivatives are added to an antisolvent to passivate the perovskite layer. The derivative can be used as a template for perovskite crystal growth in an annealing stage, and can promote the formation of a perovskite film with higher crystallization quality and larger grain size, thereby effectively improving the photoelectric conversion efficiency and stability of the device. The invention adopts the technical scheme that: an imide metal naphthalocyanine derivative has a structural general formula shown in the following formula I: wherein R is selected from the group consisting of linear alkyl, branched alkyl, linear alkoxy, branched alkoxy, linear alkylthio, branched alkylthio, alkenyl, and aryl; m is a metal selected from nickel, copper, zinc, cobalt, palladium, platinum, iron, magnesium, lead, tin, vanadium, manganese, calcium, barium or strontium. Further, the R group is straight chain alkyl or branched chain alkyl, M is metal selected from nickel, copper, zinc, cobalt, palladium, platinum, iron, magnesium, lead, tin, vanadium, manganese, calcium, barium or strontium. The structural general formula of the imide metal naphthalocyanine derivative is shown in the following formula II: in the formula II, n is 0-30, M is metal, and the metal is selected from nickel, copper, zinc, cobalt, palladium, platinum, iron, magnesium, lead, tin, vanadium, manganese, calcium, barium or strontium. Further, M is a metal selected from the group consisting of nickel, zinc, copper, iron. Specifically, the structure of the metal naphthalocyanine derivative is as follows: The reaction formula and the reaction process of the metal naphthalocyanine compound are as follows: (1) The photocatalysis bromination reaction is that under the illumination condition, the o-xylene derivative reacts with N-bromosuccinimide (NBS) under the catalysis of an initiator dibenzoyl peroxide (BPO), and the side chain on the benzene ring is brominated. (2) Diels-Alder reaction, namely under the heating condition, the brominated o-xylene derivative and dimethyl fumarate react to form a ring to obtain the 2, 3-dimethyl naphthalene derivative. (3) And (3) hydrolysis reaction, namely, under alkaline condition, carrying out hydrolysis reaction on the 2, 3-dimethyl ester naphthalene derivative, and adding hydrochloric acid for acidification after the reaction is finished to obtain the 2