The relatively high sheet resistance, low work function and poor compatibility with hole injection layers (HILs) seriously limit the applications of graphene as transparent conductive electrodes (TCEs) for organic light emitting diodes (OLEDs). Here, a graphene oxide/graphene (GO/G) vertical heterostructure is developed as TCEs for high-performance OLEDs, by directly oxidizing the top layer of three-layer graphene films with ozone treatment. Such GO/G heterostructure electrodes show greatly improved optical transmittance, a large work function, high stability, and good compatibility with HIL materials (MoO3 in this work). Moreover, the conductivity of the heterostructure is not sacrificed compared to the pristine three-layer graphene electrodes, but is significantly higher than that of pristine two-layer graphene films. In addition to high flexibility, OLEDs with different emission colors based on the GO/G heterostructure TCEs show much better performance than those based on indium tin oxide (ITO) anodes. Green OLEDs with GO/G heterostructure electrodes have the maximum current efficiency and power efficiency, as high as 82.0 cd A(-1) and 98.2 lm W(-1), respectively, which are 36.7% (14.8%) and 59.2% (15.0%) higher than those with pristine graphene (ITO) anodes. These findings open up the possibility of using graphene for next generation high-performance flexible and wearable optoelectronics with high stability.

The large surface roughness, low work function and high cost of transparent electrodes using multilayer graphene films can limit their application in organic photovoltaic (OPV) cells. Here, we develop single layer graphene (SLG) films as transparent anodes for OPV cells that contain light-absorbing layers comprised of the evaporable molecular organic semiconductor materials, zinc phthalocyanine (ZnPc)/fullerene (C60), as well as a molybdenum oxide (MoO) interfacial layer. In addition to an increase in the optical transmittance, the SLG anodes had a significant decrease in surface roughness compared to two and four layer graphene (TLG and FLG) anodes fabricated by multiple transfer and stacking of SLGs. Importantly, the introduction of a MoO interfacial layer not only reduced the energy barrier between the graphene anode and the active layer, but also decreased the resistance of the SLG by nearly ten times. The OPV cells with the structure of polyethylene terephthalate/SLG/MoO/CuI/ZnPc/C60/bathocuproine/Al were flexible, and had a power conversion efficiency of up to 0.84%, which was only 17.6% lower than the devices with an equivalent structure but prepared on commercial indium tin oxide anodes. Furthermore, the devices with the SLG anode were 50% and 86.7% higher in efficiency than the cells with the TLG and FLG anodes. These results show the potential of SLG electrodes for flexible and wearable OPV cells as well as other organic optoelectronic devices.