For the application of graphene quantum dots (GQDs) to optoelectronic nanodevices, it is of critical importance to understand the mechanisms which result in novel phenomena of their light absorption/emission. Here, we present size-dependent shape/edge-state variations of GQDs and visible photoluminescence (PL) showing anomalous size dependences. With varying the average size (d(a)) of GQDs from 5 to 35 nm, the peak energy of the absorption spectra monotonically decreases, while that of the visible PL spectra unusually shows nonmonotonic behaviors having a minimum at d(a) = ~17 nm. The PL behaviors can be attributed to the novel feature of GQDs, that is, the circular-to-polygonal-shape and corresponding edge-state variations of GQDs at d(a) = ~17 nm as the GQD size increases, as demonstrated by high-resolution transmission electron microscopy.

Coupling dissimilar oxides in heterostructures allows the engineering of interfacial, optical, charge separation/transport and transfer properties of photoanodes for photoelectrochemical (PEC) water splitting. Here, we demonstrate a double-heterojunction concept based on a BiVO/WO/SnO triple-layer planar heterojunction (TPH) photoanode, which shows simultaneous improvements in the charge transport (∼93% at 1.23 V vs RHE) and transmittance at longer wavelengths (>500 nm). The TPH photoanode was prepared by a facile solution method: a porous SnO film was first deposited on a fluorine-doped tin oxide (FTO)/glass substrate followed by WO deposition, leading to the formation of a double layer of dense WO and a WO/SnO mixture at the bottom. Subsequently, a BiVO nanoparticle film was deposited by spin coating. Importantly, the WO/(WO+SnO) composite bottom layer forms a disordered heterojunction, enabling intimate contact, lower interfacial resistance, and efficient charge transport/transfer. In addition, the top BiVO/WO heterojunction layer improves light absorption and charge separation. The resultant TPH photoanode shows greatly improved internal quantum efficiency (∼80%) and PEC water oxidation performance (∼3.1 mA/cm at 1.23 V vs RHE) compared to the previously reported BiVO/WO photoanodes. The PEC performance was further improved by a reactive-ion etching treatment and CoO electrocatalyst deposition. Finally, we demonstrated a bias-free and stable solar water-splitting by constructing a tandem PEC device with a perovskite solar cell (STH ∼3.5%).

We report substantially enhanced photoluminescence (PL) from hybrid structures of graphene/ZnO films at a band gap energy of ZnO (∼3.3  eV/376  nm). Despite the well-known constant optical conductivity of graphene in the visible-frequency regime, its abnormally strong absorption in the violet-frequency region has recently been reported. In this Letter, we demonstrate that the resonant excitation of graphene plasmon is responsible for such absorption and eventually contributes to enhanced photoemission from structures of graphene/ZnO films when the corrugation of the ZnO surface modulates photons emitted from ZnO to fulfill the dispersion relation of graphene plasmon. These arguments are strongly supported by PL enhancements depending on the spacer thickness, measurement temperature, and annealing temperature, and the micro-PL mapping images obtained from separate graphene layers on ZnO films.

Graphene quantum dots (GQDs) have received much attention due to their novel phenomena of charge transport and light absorption/emission. The optical transitions are known to be available up to ~6 eV in GQDs, especially useful for ultraviolet (UV) photodetectors (PDs). Thus, the demonstration of photodetection gain with GQDs would be the basis for a plenty of applications not only as a single-function device in detecting optical signals but also a key component in the optoelectronic integrated circuits. Here, we firstly report high-efficient photocurrent (PC) behaviors of PDs consisting of multiple-layer GQDs sandwiched between graphene sheets. High detectivity (>1011 cm Hz1/2/W) and responsivity (0.2 ~ 0.5 A/W) are achieved in the broad spectral range from UV to near infrared. The observed unique PD characteristics prove to be dominated by the tunneling of charge carriers through the energy states in GQDs, based on bias-dependent variations of the band profiles, resulting in novel dark current and PC behaviors.

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.