Super-Nernstian pH Sensor Based on Anomalous Charge Transfer Doping of Defect-Engineered Graphene.

The conventional pH sensor based on the graphene ion-sensitive field-effect transistor (Gr-ISFET), which operates with an electrostatic gating at the solution-graphene interface, cannot have a pH sensitivity above the Nernst limit (∼59 mV/pH). However, for accurate detection of the pH levels of an aqueous solution, an ultrasensitive pH sensor that can exceed the theoretical limit is required. In this study, a novel Gr-ISFET-based pH sensor is fabricated using proton-permeable defect-engineered graphene. The nanocrystalline graphene (nc-Gr) with numerous grain boundaries allows protons to penetrate the graphene layer and interact with the underlying pH-dependent charge-transfer dopant layer. We analyze the pH sensitivity of nc-Gr ISFETs by adjusting the grain boundary density of graphene and the functional group (OH-, NH2-, CH3-) on the SiO2 surface, confirming an unusual negative shift of the charge-neutral point (CNP) as the pH of the solution increases and a super-Nernstian pH response (approximately -140 mV/pH) under optimized conditions.

hBN Flake Embedded Al2O3 Thin Film for Flexible Moisture Barrier.

Due to the vulnerability of organic optoelectronic devices to moisture and oxygen, thin-film moisture barriers have played a critical role in improving the lifetime of the devices. Here, we propose a hexagonal boron nitride (hBN) embedded Al2O3 thin film as a flexible moisture barrier. After layer-by-layer (LBL) staking of polymer and hBN flake composite layer, Al2O3 was deposited on the nano-laminate template by spatial plasma atomic layer deposition (PEALD). Because the hBN flakes in Al2O3 thin film increase the diffusion path of moisture, the composite layer has a low water vapor transmission ratio (WVTR) value of 1.8 × 10-4 g/m2 day. Furthermore, as embedded hBN flakes restrict crack propagation, the composite film exhibits high mechanical stability in repeated 3 mm bending radius fatigue tests.

Defect-Free Mechanical Graphene Transfer Using n-Doping Adhesive Gel Buffer.

The synthesis of uniform low-defect graphene on a catalytic metal substrate is getting closer to the industrial level. However, its practical application is still challenging due to the lack of an appropriate method for its scalable damage-free transfer to a device substrate. Here, an efficient approach for a defect-free, etchant-free, wrinkle-free, and large-area graphene transfer is demonstrated by exploiting a multifunctional viscoelastic polymer gel as a simultaneous shock-free adhesive and dopant layer. Initially, an amine-rich polymer solution in its liquid form allows for conformal coating on a graphene layer grown on a Cu substrate. The subsequent thermally cured soft gel enables the shock-free and wrinkle-free direct mechanical exfoliation of graphene from a substrate due to its strong charge-transfer interaction with graphene and excellent shock absorption. The adhesive gel with a high optical transparency works as an electron doping layer toward graphene, which exhibits significantly reduced sheet resistances without optical transmittance loss. Lastly, the transferred graphene layer shows high mechanical and chemical stabilities under the repeated bending test and exposure to various solvents. This gel-assisted mechanical transfer method can be a solution to connect the missing part between large-scale graphene synthesis and next-generation electronics and optoelectronic applications.

Highly Efficient n-Type Doping of Graphene by Vacuum Annealed Amine-Rich Macromolecules.

Flexible transparent conducting electrodes (FTCE) are an essential component of next-generation flexible optoelectronic devices. Graphene is expected to be a promising material for the FTCE, because of its high transparency, large charge carrier mobilities, and outstanding chemical and mechanical stability. However, the electrical conductivity of graphene is still not good enough to be used as the electrode of an FTCE, which hinders its practical application. In this study, graphene was heavily n-type doped while maintaining high transmittance by adsorbing amine-rich macromolecules to graphene. The n-type charge-transfer doping of graphene was maximized by increasing the density of free amine in the macromolecule through a vacuum annealing process. The graphene adsorbed with the n-type dopants was stacked twice, resulting in a graphene FTCE with a sheet resistance of 38 ohm/sq and optical transmittance of 94.1%. The figure of merit (FoM) of the graphene electrode is as high as 158, which is significantly higher than the minimum standard for commercially available transparent electrodes (FoM = 35) as well as graphene electrodes doped with previously reported chemical doping methods. Furthermore, the n-doped graphene electrodes not only show outstanding flexibility but also maintain the doping effect even in high temperature (500 K) and high vacuum (~10-6 torr) conditions. These results show that the graphene doping proposed in this study is a promising approach for graphene-based next-generation FTCEs.

Millimeter-Scale Growth of Single-Oriented Graphene on a Palladium Silicide Amorphous Film.

It is widely accepted in condensed matter physics and material science communities that a single-oriented overlayer cannot be grown on an amorphous substrate because the disordered substrate randomizes the orientation of the seeds, leading to polycrystalline grains. In the case of two-dimensional materials such as graphene, the large-scale growth of single-oriented materials on an amorphous substrate has remained unsolved. Here, we demonstrate experimentally that the presence of uniformly oriented graphene seeds facilitates the growth of millimeter-scale single-oriented graphene with 3 × 4 mm2 on palladium silicide, which is an amorphous thin film, where the uniformly oriented graphene seeds were epitaxially grown. The amorphous palladium silicide film promotes the growth of the single-oriented growth of graphene by causing carbon atoms to be diffusive and mobile within and on the substrate. In contrast to these results, without the uniformly oriented seeds, the amorphous substrate leads to the growth of polycrystalline graphene grains. This millimeter-scale single-oriented growth from uniformly oriented seeds can be applied to other amorphous substrates.