Synthesis, optical and electroluminescent properties of novel polyfluorene/carbazole-based conjugated polyelectrolytes and their precursors

A series of novel aminoalkyl-substituted fluorene/carbazole-based main chain copolymers with benzothiadiazole (BTDZ) of different contents: poly3,6-(N-(2-ethylhexyl)carbazole)-(9,9-bis(3'-(N,N-dimethyl-amino)propyl)-2,7-fluorene)-4,7-(2,1,3-benzothiadiazole)] (PCzN-BTDZ) were synthesized by Suzuki coupling reaction. Through a postpolymerization treatment on the precursor polymer, a corresponding quaternized ammonium polyelectrolyte derivatives: poly3,6-(N-(2-ethylhexyl)carbazole)-(9,9-bis(3'-((N,N-dimethyl)-N-ethylammonium)propyl)-2,7-fluorene)-4,7-(2,l, 3-benzothiadiazole)] dibromide (PCzNBr-BTDZ) were obtained. It was found that devices from such polymers with high work-function metal cathode such as Al showed similar device performance to that by using low work-function cathode such as Ba, indicating the excellent electron injection ability of these polymers. The efficient energy transfer from fluorene-carbazole segment to the narrow band gap BTDZ site for both the neutral and the quaternized copolymers was also observed. The addition of BTDZ into the polymer main chain can also improve polymer LED (PLED) device performance. When poly(3,4-ethylenedioxythiophene) (PEDOT)/poly(vinylcarbazole) (PVK) was used as an anode buffer, the external quantum efficiency of the copolymer PCzN-BTDZ1 was 0.99%, which was much higher than the copolymer PCzN without the incorporation of BTDZ in the same device configuration.