Holt A L, Leger J M, Carter S A
Department of Physics, University of California, Santa Cruz, California 95064, USA.
J Chem Phys. 2005 Jul 22;123(4):044704. doi: 10.1063/1.1949188.
We study electrochemical p- and n-type doping in the well-known light-emitting polymer poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV). Doping reactions are characterized using cyclic voltammetry. Optical measurements including photoluminescence and UV/Vis/NIR transmission were performed on doped samples. We find that oxidation in MEH-PPV is a highly reversible reaction resulting in stable freestanding doped films, while the reduced form is unstable and the reaction irreversible. We discuss the dependence of doping reactions on scan rate, film thickness, salt type and concentration, and working electrode type. We observe the development of two additional broad absorption bands in both lightly and heavily doped films accompanied by a slight blueshift in the primary optical transition, suggesting bipolaron band formation. Finally we find that both p and n dopings result in extremely sensitive photoluminescence quenching. We propose a physical model for understanding electrochemical doping in MEH-PPV and the implications this has on the development of such technologies as polymer light-emitting electrochemical cells, electrochromic devices, actuators, and sensors.
我们研究了著名的发光聚合物聚2-甲氧基-5-(2-乙基己氧基)-1,4-亚苯基乙烯撑中的电化学p型和n型掺杂。使用循环伏安法对掺杂反应进行表征。对掺杂样品进行了包括光致发光和紫外/可见/近红外透射率在内的光学测量。我们发现,MEH-PPV中的氧化是一个高度可逆的反应,会产生稳定的独立掺杂薄膜,而还原态不稳定且反应不可逆。我们讨论了掺杂反应对扫描速率、薄膜厚度、盐的类型和浓度以及工作电极类型的依赖性。我们观察到,在轻度和重度掺杂薄膜中都出现了另外两个宽吸收带,同时初级光学跃迁略有蓝移,这表明形成了双极化子带。最后,我们发现p型和n型掺杂都会导致极其敏感的光致发光猝灭。我们提出了一个物理模型,用于理解MEH-PPV中的电化学掺杂及其对聚合物发光电化学电池、电致变色器件、致动器和传感器等技术发展的影响。