Ju Hwan Kim

High photoresponsivity in an all-graphene p – n vertical junction photodetector

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 high-efficient 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 (~10(12) cm Hz(1/2) W(-1)) and responsivity (0.4~1.0 A W(-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.

High-performance graphene-quantum-dot photodetectors

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.

Rapid-thermal-annealing surface treatment for restoring the intrinsic properties of graphene field-effect transistors

Graphene field-effect transistors (GFETs) were fabricated by photolithography and lift-off processes, and subsequently heated in a rapid-thermal-annealing (RTA) apparatus at temperatures (T(A)) from 200 to 400 °C for 10 min under nitrogen to eliminate the residues adsorbed on the graphene during the GFET fabrication processes. Raman-scattering, current-voltage (I-V), and sheet resistance measurements showed that, after annealing at 250 °C, graphene in GFETs regained its intrinsic properties, such as very small intensity ratios of D to G and G to 2D Raman bands, a symmetric I-V curve with respect to ~0 V, and very low sheet resistance. Atomic force microscopy images and height profiles also showed that the surface roughness of graphene was almost minimized at T(A) = 250 °C. By annealing at 250 °C, the electron and hole mobilities reached their maxima of 4587 and 4605 cm(2) V(-1) s(-1), respectively, the highest ever reported for chemical-vapor-deposition-grown graphene. Annealing was also performed under vacuum or hydrogen, but this was not so effective as under nitrogen. These results suggest that the RTA technique is very useful for eliminating the surface residues of graphene in GFETs, in that it employs a relatively low thermal budget of 250 °C and 10 min.

Graphene p-n vertical tunneling diodes.

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.

Near-ultraviolet-sensitive graphene/porous silicon photodetectors.

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.

Graphene/Si-nanowire heterostructure molecular sensors

Wafer-scale graphene/Si-nanowire (Si-NW) array heterostructures for molecular sensing have been fabricated by vertically contacting single-layer graphene with high-density Si NWs. Graphene is grown in large scale by chemical vapour deposition and Si NWs are vertically aligned by metal-assisted chemical etching of Si wafer. Graphene plays a key role in preventing tips of vertical Si NWs from being bundled, thereby making Si NWs stand on Si wafer separately from each other under graphene, a critical structural feature for the uniform Schottky-type junction between Si NWs and graphene. The molecular sensors respond very sensitively to gas molecules by showing 37 and 1280% resistance changes within 3.5/0.15 and 12/0.15 s response/recovery times under O2 and H2 exposures in air, respectively, highest performances ever reported. These results together with the sensor responses in vacuum are discussed based on the surface-transfer doping mechanism.

Graphene/Si‐Quantum‐Dot Heterojunction Diodes Showing High Photosensitivity Compatible with Quantum Confinement Effect

Graphene/Si quantum dot (QD) heterojunction diodes are reported for the first time. The photoresponse, very sensitive to variations in the size of the QDs as well as in the doping concentration of graphene and consistent with the quantum-confinement effect, is remarkably enhanced in the near-ultraviolet range compared to commercially available bulk-Si photodetectors. The photoresponse proves to be dominated by the carriertunneling mechanism.

Annealing effects on the characteristics of AuCl3-doped graphene

Single-layer graphene sheets grown on Cu foils by chemical vapor deposition were transferred on 300 nm SiO2/n-type Si wafers and subsequently doped with 10 mM AuCl3 solution. The doped graphene sheets were annealed at various temperatures (TA) under vacuum below 10−3 Torr for 10 min and characterized by atomic force microscopy, Raman spectroscopy, x-ray photoelectron spectroscopy (XPS), and 4-probe van der Pauw method. The XPS studies show that the compositions of Cl and Au3+ ions in doped graphene sheets increase slightly by annealing at 50 °C, but by further increase of TA above 50 °C, they monotonically decrease and become almost negligible at TA = 500 °C. These XPS results are consistent with the corresponding TA-dependent behaviors of the Raman scattering and the sheet resistance, implying that the doping efficiency is maximized at TA = 50 °C and the Cl and Au3+ ions play a major role in the doping/dedoping processes that are very reversible, different from the case of carbon nanotubes. These results...

Enhancement of the effectiveness of graphene as a transparent conductive electrode by AgNO3 doping

Single-layer graphene sheets have been synthesized by using chemical vapor deposition, and subsequently doped with AgNO₃ at various doping concentrations (n(D)) from 5 to 50 mM. Atomic force microscopy and field emission scanning electron microscopy images reveal the formation of ∼10-100 nm Ag particles on the graphene surface after doping. The type of n doping is confirmed by analyzing the n(D)-dependent behaviors of Raman scattering and the work function of the doped graphene films. The sheet resistance monotonically decreases to ∼173 Ω/sq with the increase of n(D) to 50 mM, and the transmittance is reduced by only about 3% for the highest n(D). At n(D) = 10 mM optimized doped graphene layers with a sheet resistance of 202 Ω/sq and a transmittance of 96% are obtained, resulting in a maximum DC conductivity/optical conductivity ratio (σ(DC)/σ(OP)) of ∼45.5, much larger than the minimum industry standard (σ(DC)/σ(OP) = ∼35) for transparent conductive electrodes.

Energy transfer from an individual silica nanoparticle to graphene quantum dots and resulting enhancement of photodetector responsivity

Förster resonance energy transfer (FRET), referred to as the transfer of the photon energy absorbed in donor to acceptor, has received much attention as an important physical phenomenon for its potential applications in optoelectronic devices as well as for the understanding of some biological systems. If one-atom-thick graphene is used for donor or acceptor, it can minimize the separation between donor and acceptor, thereby maximizing the FRET efficiency (EFRET). Here, we report first fabrication of a FRET system composed of silica nanoparticles (SNPs) and graphene quantum dots (GQDs) as donors and acceptors, respectively. The FRET from SNPs to GQDs with an EFRET of ∼78% is demonstrated from excitation-dependent photoluminescence spectra and decay curves. The photodetector (PD) responsivity (R) of the FRET system at 532 nm is enhanced by 100∼101/102∼103 times under forward/reverse biases, respectively, compared to the PD containing solely GQDs. This remarkable enhancement is understood by network-like current paths formed by the GQDs on the SNPs and easy transfer of the carriers generated from the SNPs into the GQDs due to their close attachment. The R is 2∼3 times further enhanced at 325 nm by the FRET effect.