聚3-己基噻吩-b-聚十六烷氧基联烯嵌段聚合物的制备及其场效应性能

Synthesis and Field Effect Transistor Performance of Poly(3-hexylthiophene)-b-poly( hexadecyloxylallene) Blockpolymer

以溴代十六烷、丙炔醇为原料通过取代反应、还原重排反应制备了十六烷氧基联烯,然后以氯化(三环己基膦)镍作为催化剂,通过控制加料顺序一锅制备了聚3-己基噻吩-b-聚十六烷氧基联烯的嵌段聚合物。通过核磁共振氢谱和体积排除色谱对产物进行了表征和确证。对聚3-己基噻吩-b-聚十六烷氧基联烯嵌段聚合物的热学性能、光学性能及电学性能进行了研究。差示扫描量热法和热重分析结果表明,嵌段共聚物具有两个玻璃化转变温度及两个热分解温度,说明其具有明显相分离。以嵌段共聚物为半导体活性材料,制备了场效应晶体管器件。使用热退火对器件进行热处理,发现迁移率随退火温度的上升而提高。器件在200℃退火温度下的平均迁移率为7.03×10^(-4)cm^2·V^(-1)·s^(-1),最大迁移率为1.3×10^(-3)cm^2·V^(-1)·s^(-1),阈值电压为5.44 V。

Hexadecyloxylallene was prepared by the substitution reaction of propargyl alcohol with bromohexadecane and the followed rearrangement reaction. Poly（ 3-hexylthiophene）-b-poly（ hexadecyloxylallene） copolymers was then synthesized in one pot via sequential addition of monomers of 3-hexylthiophene and hexadecyloxylallene by using Ni（ dppp） Cl_2 as a single catalyst. The products were confirmed by ~1H NMR and size-exclusion chromatography（ SEC）. The thermal,optical and electrical properties of the obtained block copolymer were investigated. The analysis of P3HT-b-PHA in the solid state using differential scanning calorimetry（ DSC） and thermogravimetric analysis（ TGA） revealed that the material could undergo microphase separation,as two glass transition temperatures（ T_g） and two part of the decomposition process assignable to both P3 HT and PHA phases were observed. The thin-film transistors（ TFT） with bottom-gate top-contact configuration werefabricated to characterize the electrical properties of the obtained block copolymer. The TFT devices were subsequently annealed at different temperatures（ room temperature,100,150,and 200 ℃） in a glovebox under nitrogen condition. The field-effect mobility shows an increasing trend when the annealing temperature increases. Thermal annealing is performed as an effective method to optimize the device performance because it can improve the crystallinity of the thin film. Meanwhile,thermal annealing can significantly lower the effect of the residual solvent on the carrier transport,resulting in efficient charge carrier transport. When the annealing temperature is 200 ℃,polymer-based OTFTs devices yield an average field-effect mobility of 7. 03 × 10^（-4）cm^2·V^（-1）·s^（-1）,and a maximum field-effect mobility of 1. 3 × 10^（-3）cm^2·V^（-1）·s- 1. The transfer curve shows that the threshold voltage is 5. 44 V.