Deciphering the Effect of Polymer-Assisted Doping on the Optoelectronic Properties of Block Copolymer-Anchored Graphene Oxide.

Abstract

Doping facilitates the tuning of band gap, providing an opportunity to tailor the optoelectronic properties of graphene in a simple way, and polymer-assisted doping is a new route to combine the optoelectronic properties of graphene with the properties of a polymer. In this endeavor, a linear diblock copolymer, polycaprolactone-block-poly(dimethyl aminoethyl methacrylate) (PCL13-b-PDMAEMA117) (GPCLD) is grafted from the graphene oxide (GO) surface via consecutive ring opening and atom transfer radical polymerization. GPCLD is characterized using proton nuclear magnetic resonance (1H NMR), Fourier transform infrared spectroscopy, atomic force microscopy, thermogravimetric analysis, X-ray photoelectron spectroscopy, and Raman spectroscopy. The phase transition behavior of the GPCLD solution with varying temperature and pH is monitored using fluorescence spectroscopy and dynamic light scattering. Temperature-dependent 1H NMR spectra at pH 9.2 indicate the influence of temperature on the interaction between GPCLD and solvent (water) molecules causing the phase separation. Fluorescence spectra at pH 4 and 9.2 give the evidence of localized p- and n-type doping of graphene assisted by the pendent PDMAEMA chains. In the impedance spectra of GPCLD films, the Nyquist plots vary with pH; at pH 4, they exhibit a semicircle at higher frequencies and a spike at lower frequencies; at pH 7.0, the spike is replaced by an arc; and at pH 9.2, the semicircle at higher frequencies vanishes and only a spike is noticed, all of these suggesting different types of doping of graphene at different pH values. The dc-conductivity also varies with pH and temperature because of the different types of doping. The current (I)-voltage (V) property of GPCLD at different pH values is very unique: at pH 9.2, an interesting feature of negative differential resistance (NDR) is observed; at pH 7, the rectification property is observed; and at pH 4, again the NDR property is observed. The temperature-dependent I-V property at pH 7 and 9.2 clearly indicates a signature of doping, dedoping, and redoping because of the change in the interaction of GO with the grafted polymer arising from coiling and decoiling of polymer chains.