Fluorine-substituted organic micro-molecular hole-transport material and application thereof

Abstract

The invention discloses a fluorine-substituted organic micro-molecular hole-transport material and an application thereof. The material provided by the invention has a simple molecular structure, wherein benzodithiophene and derivatives thereof are used as a central core; different heterocycle-containing units are introduced to capping groups; and the central core and the capping groups are linkedby different fluorine-substituted phenyl groups. The material provided by the invention has the advantages of simple synthesis steps, easiness in purification, good solubility in an organic solvent,proper molecular energy levels, high hole mobility and electrical conductivity, and good hydrophobicity, is applied to perovskite solar cells with good stability and high short-circuit current densityand energy conversion efficiency, and has extensive application prospects.

Description

technical field

[0001] The invention belongs to the field of organic photoelectric functional materials, in particular to a fluorine-substituted hole transport material and its application. Background technique

[0002] Organic-inorganic hybrid perovskite solar cells (PSCs) have attracted worldwide attention and research due to their high photoelectric conversion efficiency (PCE) and low fabrication cost. In recent years, the rapid development of perovskite solar cells has exceeded 22%, comparable to commercial silicon-based solar cells, showing great application prospects.

[0003] Hole transport materials (HTMs) can effectively promote hole transport and collection, reduce charge recombination, and play an important role in PSCs. 2,2',7,7'-Tetrakis(N,N-di-p-methoxyphenylamine)-9,9'-spiro-bifluorene (Spiro-OMeTAD) is currently the most widely used and most efficient spacer Cave transport material. However, Spiro-OMeTAD has many disadvantages. First of all, the synthesis...

Examples

Embodiment 1

[0047] A fluorine-substituted organic small molecule hole transport material i-1, the synthesis route is as follows:

[0048]

[0049] (1) Under nitrogen, 1,1'-[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2 ,6-diyl]bis[1,1,1-trimethyltin] (0.5g, 0.65mmol), 1,4-dibromo-2-fluorobenzene (1.0g, 3.9mmol), tetrakis(triphenyl Phosphine)palladium (Pd(PPh 3 ) 4 ) (22.5 mg, 19.5 μmol) and toluene (100 mL) were added to a 250 mL round bottom flask. React at 80°C for 6h, cool to room temperature after the reaction, dichloromethane (CH 2 Cl 2 ) extraction, the organic phase was washed with brine, anhydrous MgSO 4 Dry and concentrate by rotary evaporation to remove the solvent. Crude product with CH 2 Cl 2 and n-hexane column chromatography (hexane: CH 2 Cl 2 =4:1 (v / v)), a yellow-green intermediate (270mg, yield 53%) was obtained. 1 H NMR (400 MHz, CDCl 3 ): δ=7.655 (s, 2H), 7.634-7.561 (m, 2H), 7.499-7.471 (dd, 2H), 7.411-7.390 (d, 2H), 4.220-4.207 (d,4H), 1.88...

Embodiment 2

[0052] A fluorine-substituted organic small molecule hole transport material i-2, the synthesis route is as follows:

[0053]

[0054] (1) The process is the same as in Example 1, but the raw material 1,4-dibromo-2-fluorobenzene is replaced by 1,4-dibromo-2,5-fluorobenzene to obtain a yellow intermediate product (266mg, yield 50% ). 1 H NMR (400 MHz, CDCl 3 ): δ=7.655 (s, 2H), 7.634-7.561(m, 2H), 7.499-7.471 (dd, 2H), 7.411-7.390 (d, 2H), 4.220-4.207 (d, 4H), 1.885-1.824 (m, 2H), 1.753-1.535 (m, 8H) , 1.424 (m, 8H), 1.068-1.031 (t,6H), 0.959 (t, 6H).

[0055] (2) The process was the same as in Example 1, and an orange-yellow powder (847 mg, yield 80%) was finally obtained. 1 H NMR (400MHz, CDCl 3 ): δ=7.565 (s, 1H), 7.431-7.425 (d, 1H), 7.393 (s, 1H), 7.378-7.374(d, 1H), 7.135-7.112 (d, 3H), 7.101-7.058 (t , 2H), 7.004-6.982 (d, 6H), 6.893-6.871 (d, 3H), 6.837-6.815 (d, 6H), 4.204-4.190 (d, 4H), 3.822-3.802(d, 12H), 1.869 -1.800 (m, 2H), 1.755-1.570 (m, 8H) , 1.404 (m...

technical field

[0001] The invention belongs to the field of organic photoelectric functional materials, in particular to a fluorine-substituted hole transport material and its application. Background technique

[0002] Organic-inorganic hybrid perovskite solar cells (PSCs) have attracted worldwide attention and research due to their high photoelectric conversion efficiency (PCE) and low fabrication cost. In recent years, the rapid development of perovskite solar cells has exceeded 22%, comparable to commercial silicon-based solar cells, showing great application prospects.

[0003] Hole transport materials (HTMs) can effectively promote hole transport and collection, reduce charge recombination, and play an important role in PSCs. 2,2',7,7'-Tetrakis(N,N-di-p-methoxyphenylamine)-9,9'-spiro-bifluorene (Spiro-OMeTAD) is currently the most widely used and most efficient spacer Cave transport material. However, Spiro-OMeTAD has many disadvantages. First of all, the synthesis...

Examples

Embodiment 1

[0047] A fluorine-substituted organic small molecule hole transport material i-1, the synthesis route is as follows:

[0048]

[0049] (1) Under nitrogen, 1,1'-[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2 ,6-diyl]bis[1,1,1-trimethyltin] (0.5g, 0.65mmol), 1,4-dibromo-2-fluorobenzene (1.0g, 3.9mmol), tetrakis(triphenyl Phosphine)palladium (Pd(PPh 3 ) 4 ) (22.5 mg, 19.5 μmol) and toluene (100 mL) were added to a 250 mL round bottom flask. React at 80°C for 6h, cool to room temperature after the reaction, dichloromethane (CH 2 Cl 2 ) extraction, the organic phase was washed with brine, anhydrous MgSO 4 Dry and concentrate by rotary evaporation to remove the solvent. Crude product with CH 2 Cl 2 and n-hexane column chromatography (hexane: CH 2 Cl 2 =4:1 (v / v)), a yellow-green intermediate (270mg, yield 53%) was obtained. 1 H NMR (400 MHz, CDCl 3 ): δ=7.655 (s, 2H), 7.634-7.561 (m, 2H), 7.499-7.471 (dd, 2H), 7.411-7.390 (d, 2H), 4.220-4.207 (d,4H), 1.88...

Embodiment 2

[0052] A fluorine-substituted organic small molecule hole transport material i-2, the synthesis route is as follows:

[0053]

[0054] (1) The process is the same as in Example 1, but the raw material 1,4-dibromo-2-fluorobenzene is replaced by 1,4-dibromo-2,5-fluorobenzene to obtain a yellow intermediate product (266mg, yield 50% ). 1 H NMR (400 MHz, CDCl 3 ): δ=7.655 (s, 2H), 7.634-7.561(m, 2H), 7.499-7.471 (dd, 2H), 7.411-7.390 (d, 2H), 4.220-4.207 (d, 4H), 1.885-1.824 (m, 2H), 1.753-1.535 (m, 8H) , 1.424 (m, 8H), 1.068-1.031 (t,6H), 0.959 (t, 6H).

[0055] (2) The process was the same as in Example 1, and an orange-yellow powder (847 mg, yield 80%) was finally obtained. 1 H NMR (400MHz, CDCl 3 ): δ=7.565 (s, 1H), 7.431-7.425 (d, 1H), 7.393 (s, 1H), 7.378-7.374(d, 1H), 7.135-7.112 (d, 3H), 7.101-7.058 (t , 2H), 7.004-6.982 (d, 6H), 6.893-6.871 (d, 3H), 6.837-6.815 (d, 6H), 4.204-4.190 (d, 4H), 3.822-3.802(d, 12H), 1.869 -1.800 (m, 2H), 1.755-1.570 (m, 8H) , 1.404 (m...

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