Exchange Coupling Effects on the Magnetotransport Properties of Ni-Nanoparticle-Decorated Graphene.

We characterize the effect of ferromagnetic nickel nanoparticles (size ∼6 nm) on the magnetotransport properties of chemical-vapor-deposited (CVD) graphene. The nanoparticles were formed by thermal annealing of a thin Ni film evaporated on top of a graphene ribbon. The magnetoresistance was measured while sweeping the magnetic field at different temperatures, and compared against measurements performed on pristine graphene. Our results show that, in the presence of Ni nanoparticles, the usually observed zero-field peak of resistivity produced by weak localization is widely suppressed (by a factor of ∼3), most likely due to the reduction of the dephasing time as a consequence of the increase in magnetic scattering. On the other hand, the high-field magnetoresistance is amplified by the contribution of a large effective interaction field. The results are discussed in terms of a local exchange coupling, J∼6 meV, between the graphene π electrons and the 3d magnetic moment of nickel. Interestingly, this magnetic coupling does not affect the intrinsic transport parameters of graphene, such as the mobility and transport scattering rate, which remain the same with and without Ni nanoparticles, indicating that the changes in the magnetotransport properties have a purely magnetic origin.

Detection of Sub-fM DNA with Target Recycling and Self-Assembly Amplification on Graphene Field-Effect Biosensors.

All-electronic DNA biosensors based on graphene field-effect transistors (GFETs) offer the prospect of simple and cost-effective diagnostics. For GFET sensors based on complementary probe DNA, the sensitivity is limited by the binding affinity of the target oligonucleotide, in the nM range for 20 mer targets. We report a ∼20 000× improvement in sensitivity through the use of engineered hairpin probe DNA that allows for target recycling and hybridization chain reaction. This enables detection of 21 mer target DNA at sub-fM concentration and provides superior specificity against single-base mismatched oligomers. The work is based on a scalable fabrication process for biosensor arrays that is suitable for multiplexed detection. This approach overcomes the binding-affinity-dependent sensitivity of nucleic acid biosensors and offers a pathway toward multiplexed and label-free nucleic acid testing with high accuracy and selectivity.

All-Electronic Quantification of Neuropeptide-Receptor Interaction Using a Bias-Free Functionalized Graphene Microelectrode.

Opioid neuropeptides play a significant role in pain perception, appetite regulation, sleep, memory, and learning. Advances in understanding of opioid peptide physiology are held back by the lack of methodologies for real-time quantification of affinities and kinetics of the opioid neuropeptide-receptor interaction at levels typical of endogenous secretion (<50 pM) in biosolutions with physiological ionic strength. To address this challenge, we developed all-electronic opioid-neuropeptide biosensors based on graphene microelectrodes functionalized with a computationally redesigned water-soluble µ-opioid receptor. We used the functionalized microelectrode in a bias-free charge measurement configuration to measure the binding kinetics and equilibrium binding properties of the engineered receptor with [d-Ala2, N-MePhe4, Gly-ol]-enkephalin and ß-endorphin at picomolar levels in real time.

Crystalline Bilayer Graphene with Preferential Stacking from Ni-Cu Gradient Alloy.

We developed a high-yield synthesis of highly crystalline bilayer graphene (BLG) with two preferential stacking modes using a Ni-Cu gradient alloy growth substrate. Previously reported approaches for BLG growth include flat growth substrates of Cu or Ni-Cu uniform alloys and "copper pocket" structures. Use of flat substrates has the advantage of being scalable, but the growth mechanism is either "surface limited" (for Cu) or carbon precipitation (for uniform Ni-Cu), which results in multicrystalline BLG grains. For copper pockets, growth proceeds through a carbon back-diffusion mechanism, which leads to the formation of highly crystalline BLG, but scaling of the copper pocket structure is expected to be difficult. Here we demonstrate a Ni-Cu gradient alloy that combines the advantages of these earlier methods: the substrate is flat, so easy to scale, while growth proceeds by a carbon back-diffusion mechanism leading to high-yield growth of BLG with high crystallinity. The BLG layer stacking was almost exclusively Bernal or twisted with an angle of 30°, consistent with first-principles calculations we conducted. Furthermore, we demonstrated scalable production of transistor arrays based crystalline Bernal-stacked BLG with a band gap that was tunable at room temperature.

Scalable Production of Sensor Arrays Based on High-Mobility Hybrid Graphene Field Effect Transistors.

We have developed a scalable fabrication process for the production of DNA biosensors based on gold nanoparticle-decorated graphene field effect transistors (AuNP-Gr-FETs), where monodisperse AuNPs are created through physical vapor deposition followed by thermal annealing. The FETs are created in a four-probe configuration, using an optimized bilayer photolithography process that yields chemically clean devices, as confirmed by XPS and AFM, with high carrier mobility (3590 ± 710 cm2/V·s) and low unintended doping (Dirac voltages of 9.4 ± 2.7 V). The AuNP-Gr-FETs were readily functionalized with thiolated probe DNA to yield DNA biosensors with a detection limit of 1 nM and high specificity against noncomplementary DNA. Our work provides a pathway toward the scalable fabrication of high-performance AuNP-Gr-FET devices for label-free nucleic acid testing in a realistic clinical setting.