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CN-121974917-A - Triphenylamine gallium porphyrin complex and application thereof as hole transport material

CN121974917ACN 121974917 ACN121974917 ACN 121974917ACN-121974917-A

Abstract

The invention discloses a triphenylamine gallium porphyrin complex and application thereof as a hole transport layer material. The structure of the complex is shown in the following formula, and R represents methoxy, methylthio or hydrogen. The complex has energy level more matched with a perovskite layer and better intrinsic hole transmission characteristic, and under the condition of no chemical doping, the formal (n-i-p) perovskite solar cell prepared by the complex obtains 16.25% of photoelectric conversion efficiency, which is comparable to an early doped type Spiro-OMeTAD system. The method thoroughly abandons the lithium salt and the organic dopant which are easy to absorb and migrate, radically eliminates the degradation problem of the device caused by the lithium salt and the organic dopant, synchronously and greatly improves the long-term stability of the device under the conditions of heat, humidity and operation, greatly simplifies the preparation process, remarkably widens the process window, improves the production repeatability and the yield, directly reduces the material and the process cost and improves the industrial application potential by omitting expensive dopants, simplifying the production steps and the quality control links.

Inventors

  • ZHANG WEI
  • LI YANJIAO

Assignees

  • 陕西师范大学

Dates

Publication Date
20260505
Application Date
20260128

Claims (6)

  1. 1. The triphenylamine gallium porphyrin complex is characterized in that the structural formula of the complex is shown as follows: Wherein R represents any one of methoxy, methylthio and hydrogen.
  2. 2. Use of the triphenylamine gallium porphyrin complex according to claim 1 as a hole transport material in the preparation of perovskite solar cells.
  3. 3. The use of triphenylamine gallium porphyrin complex as a hole transport material in the preparation of perovskite solar cells according to claim 2, wherein the triphenylamine gallium porphyrin complex is dissolved in chlorobenzene to prepare a solution with the concentration of the triphenylamine gallium porphyrin complex of 4-10 mg/mL, and the solution is spin-coated on the surface of a perovskite film.
  4. 4. The use of triphenylamine gallium porphyrin complex according to claim 3 as a hole transport material in the preparation of perovskite solar cells, wherein when R in the structural formula of the triphenylamine gallium porphyrin complex represents hydrogen, the concentration of the triphenylamine gallium porphyrin complex in the solution spin-coated on the surface of the perovskite film is 4mg/mL or 10mg/mL.
  5. 5. The use of the triphenylamine gallium porphyrin complex as a hole transport material in the preparation of a perovskite solar cell according to claim 3, wherein when R in the structural formula of the triphenylamine gallium porphyrin complex represents methoxy, the concentration of the triphenylamine gallium porphyrin complex in a solution spin-coated on the surface of the perovskite film is 8-10 mg/mL.
  6. 6. The use of triphenylamine gallium porphyrin complex as a hole transport material in the preparation of perovskite solar cells according to claim 3, wherein when R in the structural formula of the triphenylamine gallium porphyrin complex represents methylthio, the concentration of the triphenylamine gallium porphyrin complex in the solution spin-coated on the surface of the perovskite film is 4-8 mg/mL.

Description

Triphenylamine gallium porphyrin complex and application thereof as hole transport material Technical Field The invention belongs to the field of perovskite photovoltaic devices, and particularly relates to an organic hole transport material and a synthesis method thereof. Background Perovskite Solar Cells (PSCs) are receiving attention because of their advantages of tunable photophysical properties, high defect tolerance, low cost of the fabrication process, etc. During the last decade, its Photoelectric Conversion Efficiency (PCE) has significantly increased from the original 3.8% to an authenticated 27.0%, with efficiency levels comparable to crystalline silicon solar cells. In PSCs, hole Transport Materials (HTM) play an important role in hole extraction and transport, interface contact quality, and device stability. To date, a large number of organic and inorganic HTMs have been developed to achieve efficient PSCs devices. In N-i-p type PSCs, 2', 7' -tetrakis (N, N-di-p-methoxyphenylamino) -9,9' -spirobifluorene (Spiro-ome tad) has been the most commonly used HTM material since 2012 because of its good energy level matching, excellent film forming properties and high reproducibility of results. However, to improve carrier mobility and conductivity of the Spiro-ome tad, dopants such as lithium bis (trifluoromethanesulfonyl) imide (LiTFSI) and 4-t-butylpyridine (t-BP) are generally introduced, and such additives accelerate performance degradation of the device under conditions of humidity, heat and optical stress, and greatly increase the synthesis cost of the hole transport layer. Therefore, the development of low cost, high mobility undoped HTMs has become a key research direction to achieve efficient stabilization of n-i-p-type PSCs. Disclosure of Invention The invention aims to overcome the defects of poor device stability, complex and uncontrollable preparation process, higher cost and the like caused by the use of hygroscopic lithium salt and a mobilizable organic additive of the traditional doped hole transport material (such as Spiro-OMeTAD), and provides a novel hole transport material and application thereof in photoelectric devices. According to the invention, a gallium (Ga) metal center is introduced into a functionalized porphyrin macrocycle to form a single component material-triphenylamine gallium porphyrin complex with matched energy level, high mobility and good stability, and the structure is as follows: wherein R represents any one of methoxy, methylthio and hydrogen. The invention also provides application of the triphenylamine gallium porphyrin complex as a hole transport layer material in perovskite solar cells. When the solution is used, the triphenylamine gallium porphyrin complex is dissolved in chlorobenzene to prepare a solution with the concentration of the triphenylamine gallium porphyrin complex of 4-10 mg/mL, and the solution is spin-coated on the surface of a perovskite film. Further, when R in the structural formula of the triphenylamine gallium porphyrin complex represents hydrogen, the concentration of the triphenylamine gallium porphyrin complex in the solution spin-coated on the surface of the perovskite film is preferably 4mg/mL or 10mg/mL. Further, when R in the structural formula of the triphenylamine gallium porphyrin complex represents methoxy, the concentration of the triphenylamine gallium porphyrin complex in the solution spin-coated on the surface of the perovskite film is preferably 8-10 mg/mL. Further, when R in the structural formula of the triphenylamine gallium porphyrin complex represents methylthio, the concentration of the triphenylamine gallium porphyrin complex in the solution spin-coated on the surface of the perovskite film is preferably 4-8 mg/mL. The beneficial effects of the invention are as follows: 1. In the aspect of device performance, the porphyrin complex constructed by the gallium metal center is introduced to realize the energy level which is more matched with the perovskite layer and the better intrinsic hole transmission characteristic, so that the formal (n-i-p) device prepared by the material obtains 16.25 percent of photoelectric conversion efficiency under the condition of no chemical doping, the performance can directly compare favorably with or even surpass the Spiro-OMeTAD system which depends on a complex doping process in the early stage, and the feasibility of realizing high efficiency without doping is proved. 2. In the aspect of device stability, the single undoped gallium porphyrin complex thoroughly abandons the lithium salt (such as Li-TFSI) which is easy to absorb moisture and the organic dopant (such as tBP) which is easy to migrate, and radically eliminates the problems of moisture absorption, phase separation and ion migration caused by the dopants, thereby synchronously and greatly improving the long-term storage stability of the device under high-temperature and high-humidity environment and the working stability