Effect of temperature on the growth of single crystalline monolayer graphene by Chemical Vapor Deposition (CVD)

Resumen del póster presentado a la 6th edition of Graphene Conference series, the largest European Event in Graphene and 2D Materials, celebrada en Genova (Italia) del 19 al 22 de abril de 2016.The ever increasing interest in graphene properties and its applications has motivated the controlled growth of high-quality graphene and fabrication of graphene-based devices. The growth of graphene via CVD using metal catalysts depends on both the intrinsic properties of the metal catalysts and the growth parameters. Here we demonstrate that the structure of single layer graphene flakes grown on a copper substrate by low pressure CVD depends dramatically on the furnace temperature, within a few tens of degrees Celsius. Optical microscope analysis of as-grown and transferred graphene onto SiO2/Si shows that growth at 1000ºC results in dendritic shapes while growth at 1040ºC gives a compact graphene flake. The low temperature growth was extended over a long time (1 hour) in order to check if there was a change in the structure towards a compact flake as the one in Figure b, which was obtained after just 10 minutes of growth time at 1040ºC. However, the size of the dendrites increased without merging. Although still poorly understood, the dendritic growth may be due to the poor smoothening of the copper at the lower annealing temperatures and to the low carbon attachment/detachment kinetics at the graphene growth fronts. We have characterized the charge and spin transport properties of the graphene grown at low temperatures. We have fabricated non-local spin valve devices with 3 μm graphene channel length and found a spin life time of 0.2 ns and spin diffusion length of 2.5 μm at room temperature. The mobility of the device was of 1000 cm2 /Vs, which is typical for CVD grown graphene on SiO2/Si. Future work will focus on comparing these results with the spintronic performance of graphene grown at higher temperatures.Peer Reviewe

Electrostatic and hydrophobic interactions involved in CNT biofunctionalization with short ss-DNA

This work is aimed at studying the adsorption mechanism of short chain 20-mer pyrimidinic homoss-DNA (oligodeoxyribonucleotide, ODN: polyC20 and polyT20) onto CNT by reflectometry. To analyze the experimental data, the effective-medium theory using the Bruggemann approximation represents a suitable optical model to account for the surface properties (roughness, thickness, and optical constants) and the size of the adsorbate. Systematic information about the involved interactions is obtained by changing the physicochemical properties of the system. Hydrophobic and electrostatic interactions are evaluated by comparing the adsorption on hydrophobic CNT and on hydrophilic silica and by modulating the ionic strength with and without Mg2+. The ODN adsorption process on CNT is driven by hydrophobic interactions only when the electrostatic repulsion is suppressed. The adsorption mode results in ODN molecules in a side-on orientation with the bases (nonpolar region) toward the surface. This unfavorable orientation is partially reverse by adding Mg2+. On the other hand, the adsorption on silica is dominated by the strong repulsive electrostatic interaction that is screened at high ionic strength or mediated by Mg2+. The cation-mediated process induces the interaction of the phosphate backbone (polar region) with the surface, leaving the bases free for hybridization. Although the general adsorption behavior of the pyrimidine bases is the same, polyC20 presents higher affinity for the CNT surface due to its acid-base properties.Authors acknowledge the financial contributions of FONCyT, SeCyT-UNC, CONICET, the International Exchange Collaboration between CAPES (Brazil) and SPU (Argentine) (Grant No. 025/05), and National Institute of General Medical Sciences (NIGMS)/National Institutes of Health (1SC3GM081085) (C.D.G). M.J.E. thanks the Ministry of Education and Science of Spain (Project NAN2004-093006-C05-03) and the “Ramón and Cajal” Program. M.L.C. thanks CONICET for the fellowship granted.Peer Reviewe

Exciton tuning and strain imaging in WS2supported on PDMS micropillars

Since the raise of 2D materials, significant research has been dedicated to their strain-dependent electronic and mechanical properties. In this work, we studied exciton energies and low-frequency phonon modes in CVD-grown mono- and few-layer WS2 transferred on PDMS micropillars. The modification of the band structure under strain was investigated by photoluminescence (PL) spectroscopy at room temperature. Machine learning (ML) methods were used to analyze the PL spatial maps and facilitate the spectral deconvolution. For monolayer (1L) WS2, red shift in the exciton energy was detected as a function of the position, which was ascribed to the presence of residual strain. For three-layer (3L) strained WS2, a significant increase in the PL intensity corresponding to direct (K-K) band transition together with a change of exciton energy was observed. From the PL spectra, strain distribution maps were extracted for both studied samples, which strongly resembled the ML clustering results. Finally, the low-frequency Raman modes of WS2 were studied on both Si/SiO2 and PDMS substrates and no significant change of their frequency was observed for the 3L-WS2.This work has been supported by the Severo Ochoa Program (No. SEV-2017-0706 funded by MCIN/AEI/10.13039/501100011033), by the Spanish Ministry of Economy and Competitiveness (MINECO) under Contract Nos. PGC2018-095032-B-I00 and PID2021-124568NB-I00, and by the CERCA Programme/Generalitat de Catalunya. The authors acknowledge the European Union's H2020 FET Proactive Project TOCHA (Grant No. 824140) and the ERC-AdG Project LEIT (Grant No. 885689)

Impact of the in situ rise in hydrogen partial pressure on graphene shape evolution during CVD growth of graphene

Exposing graphene to a hydrogen post-etching process yields dendritic graphene shapes. Here, we demonstrate that similar dendritic structures can be achieved at long growth times without adding hydrogen externally. These shapes are not a result of a surface diffusion controlled growth but of the competing backward reaction (etching), which dominates the growth dynamics at long times due to an in situ rise in the hydrogen partial pressure. We have performed a systematic study on the growth of graphene as a function of time to identify the onset and gradual evolution of graphene shapes caused by etching and then demonstrated that the etching can be stopped by reducing the flow of hydrogen from the feed. In addition, we have found that the etching rate due to the in situ rise in hydrogen is strongly dependent on the confinement (geometrical confinement) of copper foil. Highly etched graphene with dendritic shapes was observed in unconfined copper foil regions while no etching was found in graphene grown in a confined reaction region. This highlights the effect of the dynamic reactant distribution in activating the in situ etching process during growth, which needs to be counteracted or controlled for large scale growth.This research was partially supported by the Spanish Ministry of Economy and Competitiveness, MINECO (under Contracts No. MAT2013-46785-P, No. MAT2016-75952-R, No. MAT2015-68307- P and Severo Ochoa No. SEV-2013-0295), by the European Research Council under Grant Agreement No. 306652 SPINBOUND, by the European Union's Horizon 2020 research and innovation programme under grant agreement No. 696656, and by the CERCA Programme and the Secretariat for Universities and Research, Knowledge Department of the Generalitat de Catalunya 2014 SGR 56. ZMG acknowledges support from MINECO FPI fellowship under Contract No. BES-2014-069925.Peer reviewe

Electrocatalytic tuning of biosensing response through electrostatic or hydrophobic enzyme-graphene oxide interactions

The effect of graphene oxidative grades upon the conductivity and hydrophobicity and consequently the influence on an enzymatic biosensing response is presented. The electrochemical responses of reduced graphene oxide (rGO) have been compared with the responses obtained from the oxide form (oGO) and their performances have been accordingly discussed with various evidences obtained by optical techniques. We used tyrosinase enzyme as a proof of concept receptor with interest for phenolic compounds detection through its direct adsorption onto a screen-printed carbon electrode previously modified with oGO or rGO with a carbon-oxygen ratio of 1.07 or 1.53 respectively. Different levels of oGO directly affect the (bio)conjugation properties of the biosensor due to changes at enzyme/graphene oxide interface coming from the various electrostatic or hydrophobic interactions with biomolecules. The developed biosensor was capable of reaching a limit of detection of 0.01. nM catechol. This tuning capability of the biosensor response can be of interest for building several other biosensors, including immunosensors and DNA sensors for various applications. © 2014 Elsevier B.V.MEC (Spain) for MAT2011-25870 grant is acknowledged.Peer Reviewe