CN-117865990-B - Non-condensed ring thiophene polynuclear hole transport material and preparation method and application thereof

Abstract

The invention belongs to the technical field of organic synthesis, and discloses a non-condensed ring thiophene polynuclear hole transport material, and a preparation method and application thereof. The hole transport material takes non-condensed ring thiophene polynuclear as a central core, methoxy triphenylamine as a peripheral end group, and S and O atoms of the non-condensed ring thiophene polynuclear are favorable for forming a non-covalent conformational lock effect, so that the material has excellent dissolving film-forming property, and meanwhile, the molecular accumulation can be effectively enhanced, and the hole transport property is improved. In addition, the interface effect of the hole transport layer and the perovskite layer is promoted by the characteristic of the central core polysulfide atoms, so that interface defects of the perovskite layer are passivated, and the carrier transport and separation efficiency is further improved. The non-condensed ring thiophene polynuclear hole transport material is applied to perovskite solar cells, the open circuit voltage of the device is 1.130V, the short circuit photocurrent density is 24.07 mA cm ‑2 , the filling factor is 0.7860, and the photoelectric conversion efficiency which is up to 21.38% is finally obtained, so that the material has huge commercial application value.

Inventors

• WANG ZHE
• MA CHAOLONG
• YAN DINGDING
• LIU YAN
• QIAN WEI
• CHEN JINGZHONG
• XU YANGYANG
• WANG ZHIHUI
• YU CHUNHAO

Assignees

• 淮阴工学院

Dates

Publication Date

20260508

Application Date

20231205

Claims (8)

1. 1. A non-condensed ring thiophene polynuclear hole transport material is characterized by having a molecular structural formula shown in FR 01: 。
2. 2. The method for preparing the non-planar thiophene polynuclear hole transport material according to claim 1, comprising the following steps: (1) Brominating the compound 1 to generate an intermediate 2; (2) Coupling compound 3 with compound 4 to form intermediate 5; (3) The intermediate 5 is subjected to substitution reaction to generate an intermediate 6; (4) Enabling the intermediate 2 and the intermediate 6 to generate a compound FR01 through Stille coupling reaction, namely the non-planar thiophene polynuclear hole transport material; The reaction equation is shown below: 。
3. 3. The preparation method of the non-planar thiophene polynuclear hole transport material is characterized in that the specific process of the step (1) is that a compound 1 and N-bromosuccinimide (NBS) are subjected to bromination reaction in tetrahydrofuran solvent to generate an intermediate 2, and the molar ratio of the compound 1 to the NBS is 1:2-3.
4. 4. The preparation method of the non-condensed ring thiophene polynuclear hole transport material is characterized by comprising the specific process of the step (2), wherein a compound 3, a compound 4, potassium carbonate, pivalic acid, palladium acetate and tris (o-methylphenyl) phosphorus are mixed and dissolved in N, N-Dimethylformamide (DMF), heating reaction is carried out in a nitrogen atmosphere, and after the reaction is finished, an intermediate 5 is obtained through separation and purification, wherein the molar ratio of the compound 3 to the compound 4 to the palladium acetate to the tris (o-methylphenyl) phosphorus to the pivalic acid to the potassium carbonate is 1:2-3:0.1-0.2:0.2-0.4:0.2-1:1-2.
5. 5. The preparation method of the non-planar thiophene polynuclear hole transport material is characterized by comprising the specific process of the step (3), wherein an intermediate 5 is dissolved in anhydrous tetrahydrofuran, n-hexane solution of n-butyllithium is dropwise added under the cooling condition, stirring is continuously carried out at a low temperature, tributyltin chloride is added, the reaction solution is heated to room temperature, stirring is continued for reaction overnight, water quenching is carried out after the reaction is finished, the organic solvent is extracted and dried, and the solvent is removed under reduced pressure to obtain an intermediate 6, wherein the molar ratio of the intermediate 5 to the n-butyllithium to the tributyltin chloride is 1:1.1-1.5:1-1.5.
6. 6. The preparation method of the non-planar thiophene polynuclear hole transport material is characterized in that the specific process of the step (4) is that an intermediate 2, an intermediate 6 and Pd (PPh 3 ) 4 ) are mixed and dissolved in toluene, heating reflux reaction is carried out in a nitrogen atmosphere, after the reaction is finished, a compound FR01 is obtained through separation and purification, and the molar ratio of the intermediate 2 to the intermediate 6 to the Pd (PPh 3 ) 4 is 1:2-3:0.05-0.1.
7. 7. The preparation method of the non-condensed ring thiophene polynuclear hole transport material according to claim 5, wherein the reaction temperature in the step (1) is 25 ℃, the reaction time is 8h ℃, the reaction temperature in the step (2) is 100 ℃, the reaction time is 36 h, the temperature of dropwise adding n-butyllithium and continuous stirring in the step (3) is-78 ℃, the continuous stirring time is 2h, and the reaction temperature in the step (4) is 110 ℃ and the reaction time is 12h.
8. 8. The use of a non-condensed ring thiophene polynuclear hole transport material according to claim 1 in perovskite solar cells.

Description

Non-condensed ring thiophene polynuclear hole transport material and preparation method and application thereof Technical Field The invention belongs to the technical field of organic synthesis, relates to synthesis of a hole transport material, and in particular relates to a non-condensed ring thiophene polynuclear hole transport material, and a preparation method and application thereof Background As a new generation of photovoltaic technology, perovskite solar cells (Perovskite Solar Cells, PSCs for short) have the advantages of simple preparation process, easily-modulated materials, low cost and the like, and the latest authentication efficiency has reached 26.2% (National Renewable Energy Laboratory, NREL, 2023). Typical PSCs devices consist essentially of conductive glass, electron transport layers, perovskite films, hole Transport Materials (HTMs), and metal electrodes. The hole transport material mainly collects and transports photo-generated holes, inhibits interface electron recombination and realizes high-efficiency separation and transport of electrons and holes. Thus, high performance HTMs are critical to the performance of the device. Organic micromolecular hole transport materials are attracting attention because of simple synthesis, flexible structural design and high photoelectric conversion efficiency. Organic small molecule HTMs typically employ a "central core + peripheral end group" construction strategy. The performance of the hole transport material can be effectively improved by regulating and optimizing the molecular center core. Among them, HTMs based on a Spiro group as a central core (e.g., spiro-ome tad) exhibit excellent solubility and high quality film morphology, and have been receiving attention. However, the HTMs inhibit intermolecular interaction due to the non-planar three-dimensional configuration, reduce hole transmission efficiency, and require doping additives such as lithium salt, cobalt salt, tert-butylpyridine and the like, so that the preparation cost of the battery is increased, the stability of the device is reduced, and the materials are difficult to purify and have high price. In view of the shortcomings of the spiro central core, researchers have in turn developed HTMs based on planar central cores. The introduction of the planar rigid center core promotes the electron dipole action of hole molecules, and effectively improves the hole mobility. However, the high conjugation of the central core likewise leads to a decrease in the dissolved film-forming properties. Therefore, the trade-off effect between the dissolution film-forming property and the hole mobility is a bottleneck for limiting the further improvement of the performance of the small molecule hole transport material. Therefore, it is important to develop novel small-molecule HTMs with excellent dissolution film-forming property and high-efficiency hole transport property. Disclosure of Invention Aiming at the defects of the prior art, the invention aims to provide a non-condensed ring thiophene polynuclear hole transport material, and a preparation method and application thereof. The non-condensed ring thiophene central core in the HTMs is beneficial to ensuring that the materials have excellent solubility in solvents, thereby being beneficial to improving the film forming quality of the HTMs. Meanwhile, noncovalent conformation locking effect can be formed between S, O atoms in the central core, so that the HTMs form a planarized molecular space configuration in the film forming process, the intermolecular interaction is enhanced, and the hole transport and extraction performance of the hole transport material is further improved. In addition, the characteristic of the central core polysulfide atoms promotes the interface action of the hole transport layer and the perovskite layer, is beneficial to passivation of interface defects of the perovskite layer, and improves the electron-hole transport separation efficiency. The non-condensed ring thiophene polynuclear hole transport material is applied to perovskite solar cells, the photoelectric conversion efficiency of the device can be up to 21.38%, and the material has high-efficiency device stability and high commercial application value. The invention is realized by the following technical scheme: A non-condensed ring thiophene polynuclear hole transport material has a molecular structural formula shown in FR 01: 。 the invention further improves the scheme as follows: the preparation method of the non-planar thiophene polynuclear hole transport material comprises the following steps: (1) Brominating the compound 1 to generate an intermediate 2; (2) Coupling compound 3 with compound 4 to form intermediate 5; (3) The intermediate 5 is subjected to substitution reaction to generate an intermediate 6; (4) Enabling the intermediate 2 and the intermediate 6 to generate a compound FR01 through Stille coupling reaction, namely the non-planar thiophene pol