Graphene has demonstrated great promise for technological use, yet control over material growth and understanding of how material imperfections affect the performance of devices are challenges that hamper the development of applications. In this work, we reveal new insight into the connections between the performance of the graphene devices as environmental sensors and the microscopic details of the interactions at the sensing surface. We monitor changes in the resistance of the chemical-vapor deposition grown graphene devices as exposed to different concentrations of ethanol. We perform thermal surface treatments after the devices are fabricated, use scanning probe microscopy to visualize their effects down to nanometer scale and correlate them with the measured performance of the device as an ethanol sensor. Our observations are compared to theoretical calculations of charge transfers between molecules and the graphene surface. We find that, although often overlooked, the surface cleanliness after device fabrication is responsible for the device performance and reliability. These results further our understanding of the mechanisms of sensing in graphene-based environmental sensors and pave the way to optimizing such devices, especially for their miniaturization, as with decreasing size of the active zone the potential role of contaminants will rise.

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Spectroscopic, photophysical and computational studies designed to expose and explain the differences in the efficiencies of non-coherent photon upconversion (NCPU) by triplet-triplet annihilation (TTA) have been carried out for a new series of alkyl-substituted diphenyl and tetraphenyl zinc porphyrins, both in fluid solution and in solid films. Systematic variations in the alkyl-substitution of the phenyl groups in both the di- and tetraphenyl porphyrins introduces small, but well-understood changes in their spectroscopic and photophysical properties and in their TTA efficiencies. In degassed toluene solution TTA occurs for all derivatives and produces the fluorescent S product states in all cases. In PVA matrices, however, none of the di-phenylporphyrins exhibit measurable NCPU whereas all the tetraphenyl-substituted compounds remain upconversion-active. In PVA the NCPU efficiencies of the zinc tetraphenylporphyrins vary significantly with their steric characteristics; the most sterically crowded tetraphenyl derivative exhibits the greatest efficiency. DFT-D computations have been undertaken and help reveal the sources of these differences.

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