Nanoscale Direct Mapping of Noise Source Activities on Graphene Domains

An electrical noise is one of the key parameters determining the performance of modern electronic devices. However, it has been extremely difficult, if not impossible, to image localized noise sources or their activities in such devices. We report a “noise spectral imaging” strategy to map the activities of localized noise sources in graphene domains. Using this method, we could quantitatively estimate sheet resistances and noise source densities inside graphene domains, on domain boundaries and on the edge of graphene. The results show high activities of noise sources and large sheet resistance values at the domain boundary and edge of graphene. Additionally, we showed that the top layer in double-layer graphene had lower noises than single-layer graphene. This work provides valuable insights about the electrical noises of graphene. Furthermore, the capability to directly map noise sources in electronic channels can be a major breakthrough in electrical noise research in general

Strain-Assisted Wafer-Scale Nanoperforation of Single-Layer Graphene by Arrayed Pt Nanoparticles

We demonstrate the large-area lithography-free ordered perforation of reduced graphene oxide (rGO) and graphene grown by chemical vapor deposition (CVD) with arrayed Pt nanoparticles (NPs) prepared by using self-patterning diblock copolymer micelles. The rGO layers were perforated by Pt NPs formed either on top or bottom surface. On the other hand, CVD graphene was perforated only when the Pt NPs were placed under the graphene layer. Various control experiments confirm that the perforation reaction of CVD graphene was catalyzed by Pt NPs, where the mechanical strain as well as the chemical reactivity of Pt lowered the activation energy barriers for the oxidation reaction of CC bonds in graphene. Systematic atomic force microscopy and Raman analyses revealed the detailed perforation mechanism. The pore size and spacing can be controlled, and thus our present work may open a new direction in the development of ordered nanopatterns on graphene using metal NPs

Optical Probing of the Electronic Interaction between Graphene and Hexagonal Boron Nitride

Even weak van der Waals (vdW) adhesion between two-dimensional solids may perturb their various materials properties owing to their low dimensionality. Although the electronic structure of graphene has been predicted to be modified by the vdW interaction with other materials, its optical characterization has not been successful. In this report, we demonstrate that Raman spectroscopy can be utilized to detect a few percent decrease in the Fermi velocity (<i>v</i>_F) of graphene caused by the vdW interaction with underlying hexagonal boron nitride (hBN). Our study also establishes Raman spectroscopic analysis which enables separation of the effects by the vdW interaction from those by mechanical strain or extra charge carriers. The analysis reveals that spectral features of graphene on hBN are mainly affected by change in <i>v</i>_F and mechanical strain but not by charge doping, unlike graphene supported on SiO₂ substrates. Graphene on hBN was also found to be less susceptible to thermally induced hole doping

Strain Relaxation of Graphene Layers by Cu Surface Roughening

The surface morphology of copper (Cu) often changes after the synthesis of graphene by chemical vapor deposition (CVD) on a Cu foil, which affects the electrical properties of graphene, as the Cu step bunches induce the periodic ripples on graphene that significantly disturb electrical conduction. However, the origin of the Cu surface reconstruction has not been completely understood yet. Here, we show that the compressive strain on graphene induced by the mismatch of thermal expansion coefficient with Cu surface can be released by forming periodic Cu step bunching that depends on graphene layers. Atomic force microscopy (AFM) images and the Raman analysis show the noticeably longer and higher step bunching of Cu surface under multilayer graphene and the weaker biaxial compressive strain on multilayer graphene compared to monolayer. We found that the surface areas of Cu step bunches under multilayer and monolayer graphene are increased by ∼1.41% and ∼0.77% compared to a flat surface, respectively, indicating that the compressive strain on multilayer graphene can be more effectively released by forming the Cu step bunching with larger area and longer periodicity. We believe that our finding on the strain relaxation of graphene layers by Cu step bunching formation would provide a crucial idea to enhance the electrical performance of graphene electrodes by controlling the ripple density of graphene

Vapor-Phase Molecular Doping of Graphene for High-Performance Transparent Electrodes

Doping is an essential process to engineer the conductivity and work-function of graphene for higher performance optoelectronic devices, which includes substitutional atomic doping by reactive gases, electrical/electrochemical doping by gate bias, and chemical doping by acids or reducing/oxidizing agents. Among these, the chemical doping has been widely used due to its simple process and high doping strength. However, it also has an instability problem in that the molecular dopants tend to gradually evaporate from the surface of graphene, leading to substantial decrease in doping effect with time. In particular, the instability problem is more serious for n-doped graphene because of undesirable reaction between dopants and oxygen or water in air. Here we report a simple method to tune the electrical properties of CVD graphene through n-doping by vaporized molecules at 70 °C, where the dopants in vapor phase are mildly adsorbed on graphene surface without direct contact with solution. To investigate the dependence on functional groups and molecular weights, we selected a series of ethylene amines as a model system, including ethylene diamine (EDA), diethylene triamine (DETA), and triethylene tetramine (TETA) with increasing number of amine groups showing different vapor pressures. We confirmed that the vapor-phase doping provides not only very high carrier concentration but also good long-term stability in air, which is particularly important for practical applications

Roll-to-Roll Laser-Printed Graphene–Graphitic Carbon Electrodes for High-Performance Supercapacitors

Carbon electrodes including graphene and thin graphite films have been utilized for various energy and sensor applications, where the patterning of electrodes is essentially included. Laser scribing in a DVD writer and inkjet printing were used to pattern the graphene-like materials, but the size and speed of fabrication has been limited for practical applications. In this work, we devise a simple strategy to use conventional laser-printer toner materials as precursors for graphitic carbon electrodes. The toner was laser-printed on metal foils, followed by thermal annealing in hydrogen environment, finally resulting in the patterned thin graphitic carbon or graphene electrodes for supercapacitors. The electrochemical cells made of the graphene–graphitic carbon electrodes show remarkably higher energy and power performance compared to conventional supercapacitors. Furthermore, considering the simplicity and scalability of roll-to-roll (R2R) electrode patterning processes, the proposed method would enable cheaper and larger-scale synthesis and patterning of graphene–graphitic carbon electrodes for various energy applications in the future

Solution-Processed n‑Type Graphene Doping for Cathode in Inverted Polymer Light-Emitting Diodes

n-Type doping with (4-(1,3-dimethyl-2,3-dihydro-1H-benzoimidazol-2-yl)­phenyl) dimethylamine (N-DMBI) reduces a work function (WF) of graphene by ∼0.45 eV without significant reduction of optical transmittance. Solution process of N-DMBI on graphene provides effective n-type doping effect and air-stability at the same time. Although neutral N-DMBI act as an electron receptor leaving the graphene p-doped, radical N-DMBI acts as an electron donator leaving the graphene n-doped, which is demonstrated by density functional theory. We also verify the suitability of N-DMBI-doped n-type graphene for use as a cathode in inverted polymer light-emitting diodes (PLEDs) by using various analytical methods. Inverted PLEDs using a graphene cathode doped with N-DMBI radical showed dramatically improved device efficiency (∼13.8 cd/A) than did inverted PLEDs with pristine graphene (∼2.74 cd/A). N-DMBI-doped graphene can provide a practical way to produce graphene cathodes with low WF in various organic optoelectronics

Graphene–Ferroelectric Hybrid Structure for Flexible Transparent Electrodes

Graphene has exceptional optical, mechanical, and electrical properties, making it an emerging material for novel optoelectronics, photonics, and flexible transparent electrode applications. However, the relatively high sheet resistance of graphene is a major constraint for many of these applications. Here we propose a new approach to achieve low sheet resistance in large-scale CVD monolayer graphene using nonvolatile ferroelectric polymer gating. In this hybrid structure, large-scale graphene is heavily doped up to 3 × 10¹³ cm^–2 by nonvolatile ferroelectric dipoles, yielding a low sheet resistance of 120 Ω/□ at ambient conditions. The graphene–ferroelectric transparent conductors (GFeTCs) exhibit more than 95% transmittance from the visible to the near-infrared range owing to the highly transparent nature of the ferroelectric polymer. Together with its excellent mechanical flexibility, chemical inertness, and the simple fabrication process of ferroelectric polymers, the proposed GFeTCs represent a new route toward large-scale graphene-based transparent electrodes and optoelectronics

Balancing Light Absorptivity and Carrier Conductivity of Graphene Quantum Dots for High-Efficiency Bulk Heterojunction Solar Cells

Graphene quantum dots (GQDs) have been considered as a novel material because their electronic and optoelectronic properties can be tuned by controlling the size and the functional groups of GQDs. Here we report the synthesis of reduction-controlled GQDs and their application to bulk heterojunction (BHJ) solar cells with enhanced power conversion efficiency (PCE). Three different types of GQDsgraphene oxide quantum dots (GOQDs), 5 h reduced GQDs, and 10 h reduced GQDswere tested in BHJ solar cells, and the results indicate that GQDs play an important role in increasing optical absorptivity and charge carrier extraction of the BHJ solar cells. The enhanced optical absorptivity by rich functional groups in GOQDs increases short-circuit current, while the improved conductivity of reduced GQDs leads to the increase of fill factors. Thus, the reduction level of GQDs needs to be intermediate to balance the absorptivity and conductivity. Indeed, the partially reduced GQDs yielded the outstandingly improved PCE of 7.60% in BHJ devices compared to a reference device without GQDs (6.70%)

Work-Function Engineering of Graphene Electrodes by Self-Assembled Monolayers for High-Performance Organic Field-Effect Transistors

We have devised a method to optimize the performance of organic field-effect transistors (OFETs) by controlling the work functions of graphene electrodes by functionalizing the surface of SiO₂ substrates with self-assembled monolayers (SAMs). The electron-donating NH₂-terminated SAMs induce strong n-doping in graphene, whereas the CH₃-terminated SAMs neutralize the p-doping induced by SiO₂ substrates, resulting in considerable changes in the work functions of graphene electrodes. This approach was successfully utilized to optimize electrical properties of graphene field-effect transistors and organic electronic devices using graphene electrodes. Considering the patternability and robustness of SAMs, this method would find numerous applications in graphene-based organic electronics and optoelectronic devices such as organic light-emitting diodes and organic photovoltaic devices