Graphene has some drawbacks, like the absence of an electronic band gap which leads to only small gate switching ratios, and its fast carrier recombination that limits its use in optoelectronics. In order to overcome these issues, the aim of this thesis was to tune the properties of graphene by two different modification approaches. The first approach involved chemical functionalization to create lateral graphene heterostructures, whereas the second approach was directed toward vertical heterostructures that combine graphene with another 2D material. For the former case, two novel chemical functionalization methods were investigated. The first method relied upon hyperthermal molecular ion collisions with 4,4¿-azobis(pyridine). This enabled the covalent functionalization of graphene with a functionalization degree of up to 3%, as demonstrated by Raman in combination with XPS. AFM studies revealed that the functionalized sheets retain their topographic integrity. Thus obtained stripe-like patterns of covalently graphene within extended graphene sheets enabled enhanced on/off ratios upon gate switching. In the second functionalization, OsO4 was used to selectively introduce hydroxyl groups to graphene. Best results were obtained using UV light activation, which yielded graphene of high covalent functionalization degree, as concluded from its optical transparency and gate-induced on/off switching ratios of up to 500. Temperature dependent electrical measurements revealed 2D hopping as the dominant transport mechanism. The first type of vertical heterostructure, gr-TiOx-Ti diodes were fabricated and their electrical properties in the dark and under visible light illumination studied. In contrast to conventional MIM diodes, the performance of the graphene-based diodes was found to increase with decreasing thickness of the oxide insulator. Bias-induced modulation of the work function of graphene was identified as the key to the operation mechanism of the graphene diodes, enabling them to reach a very high asymmetry and nonlinearity (9000 and 8). The diodes compete well with state-of-the-art MIM diodes. Furthermore, the graphene-TiOx-Ti diodes could be operated as photovoltaic cell, with a maximum open-circuit voltage of 0.3 V and a short-circuit photocurrent of 14 nA under global illuminationt. This finding constitutes the first proof-of-principle of hot carrier extraction from graphene, based on the photovoltaic effect. The second type of vertical heterostructures was based on black phosphorus (BP). As a first step, thin BP sheets were combined with n-GaAs into novel pn devices. They displayed pronounced rectification behavior that, in the low bias regime, approaches that of ideal diodes. Moreover, when operated as photodiodes they reached external quantum efficiencies (EQE) above 30% under higher reverse bias. On this basis, the bP was then combined with gr into a p+/p heterojunction. Thus obtained devices achieved a maximum internal quantum efficiency (IQE) and responsivity of 13% and 10.7 mA/W, respectively. This IQE is the highest thus far reported for diodes comprising BP and another 2D material. Moreover, with the aid of a top gate it was possible to modulate both, the photo-conversion efficiency and photocurrent generation mechanism of the black phosphorous-graphene diodes. Together with the possibility to tune the photocurrent response by the thickness of the black phosphorous, these diodes emerge as promising photodetectors.
EPFL2016
