Intensive studies have recently been performed on graphene-based photodetectors, but most of them are based on field effect transistor structures containing mechanically exfoliated graphene, not suitable for practical large-scale device applications. Here we report highefficient photodetector behaviours of chemical vapor deposition grown all-graphene p-n vertical-type tunnelling diodes. The observed photodetector characteristics well follow what are expected from its band structure and the tunnelling of current through the interlayer between the metallic p-and n-graphene layers. High detectivity (B10 12 cm Hz 1/2 W À 1 ) and responsivity (0.4B1.0 A W À 1 ) are achieved in the broad spectral range from ultraviolet to near-infrared and the photoresponse is almost consistent under 6-month operations. The high photodetector performance of the graphene p-n vertical diodes can be understood by the high photocurrent gain and the carrier multiplication arising from impact ionization in graphene.

Raman-scattering behaviors have been studied in graphene quantum dots (GQDs) by varying their average size (d) from 5 to 35 nm. The peak frequencies of D and 2D bands are almost irrespective of d, and the intensity of the D band is larger than that of the G band over almost full range of d. These results suggest that GQDs are defective, possibly resulting from the dominant contributions from the edge states at the periphery of GQDs. The G band shows a maximum peak frequency at d = ∼17 nm, whilst the full-width half maximum of the G band and the peak-intensity ratio of the D to G bands are minimized at d = ∼17 nm. Since the average thickness of GQDs (t) is proportional to d, t can act as a factor affecting the d-dependent Raman-scattering behaviors, but they cannot be explained solely by the t variation. We propose that the abrupt changes in the Raman-scattering behaviors of GQDs at d = ∼17 nm originate from size-dependent edge-state variation of GQDs at d = ∼17 nm as d increases.

Formation and characterization of graphene p-n junctions are of particular interest because the p-n junctions are used in a wide variety of electronic/photonic systems as building blocks. Graphene p-n junctions have been previously formed by using several techniques, but most of the studies are based on lateral-type p-n junctions, showing no rectification behaviors. Here, we report a new type of graphene p-n junction. We first fabricate and characterize vertical-type graphene p-n junctions with two terminals. One of the most important characteristics of the vertical junctions is the asymmetric rectifying behavior showing an on/off ratio of ~10(3) under bias voltages below ±10 V without gating at higher n doping concentrations, which may be useful for practical device applications. In contrast, at lower n doping concentrations, the p-n junctions are ohmic, consistent with the Klein-tunneling effect. The observed rectification results possibly from the formation of strongly corrugated insulating or semiconducting interlayers between the metallic p- and n-graphene sheets at higher n doping concentrations, which is actually a structure like a metal-insulator-metal or metal-semiconductor-metal tunneling diode. The properties of the diodes are almost invariant even 6 months after fabrication.

Porous silicon (PSi) is recognized as an attractive building block for photonic devices because of its novel properties including high ratio of surface to volume and high light absorption. We first report near-ultraviolet (UV)-sensitive graphene/PSi photodetectors (PDs) fabricated by utilizing graphene and PSi as a carrier collector and a photoexcitation layer, respectively. Thanks to high light absorption and enlarged energy-band gap of PSi, the responsivity (Ri) and quantum efficiency (QE) of the PDs are markedly enhanced in the near-UV range. The performances of PDs are systemically studied for various porosities of PSi, controlled by varying the electroless-deposition time (td) of Ag nanoparticles for the use of Si etching. Largest gain is obtained at td = 3 s, consistent with the maximal enhancement of Ri and QE in the near UV range, which originates from the well-defined interface at the graphene/PSi junction, as proved by atomic- and electrostatic-force microscopies. Optimized response speed is ∼10 times faster compared to graphene/single-crystalline Si PDs. These and other unique PD characteristics prove to be governed by typical Schottky diode-like transport of charge carriers at the graphene/PSi junctions, based on bias-dependent variations of the band profiles, resulting in novel dark- and photocurrent behaviors.

Nonvolatile flash-memory capacitors containing graphene quantum dots (GQDs) of 6, 12, and 27 nm average sizes (d) between SiO2 layers for use as charge traps have been prepared by sequential processes: ion-beam sputtering deposition (IBSD) of 10 nm SiO2 on a p-type wafer, spin-coating of GQDs on the SiO2 layer, and IBSD of 20 nm SiO2 on the GQD layer. The presence of almost a single array of GQDs at a distance of ∼13 nm from the SiO2/Si wafer interface is confirmed by transmission electron microscopy and photoluminescence. The memory window estimated by capacitance-voltage curves is proportional to d for sweep voltages wider than  ± 3 V, and for d = 27 nm the GQD memories show a maximum memory window of 8 V at a sweep voltage of  ± 10 V. The program and erase speeds are largest at d = 12 and 27 nm, respectively, and the endurance and data-retention properties are the best at d = 27 nm. These memory behaviors can be attributed to combined effects of edge state and quantum confinement.