Raman Spectroscopy Study of Graphene Under High Pressure

Due to its exceptional mechanical and electrical properties, graphene (one layer sheet of carbon atoms) has attracted a lot of attention since its discovery in 2004. The purpose of this research is to compare the Raman spectra of graphene with plasma treated graphene sheets which have been treated by changing the different parameters affecting the plasma treatment like gas flow, power and pressure and treatment time. The graphene we used for our high pressure studies are 4-5 layer CVD deposited graphene samples prepared by our collaborators in Dr. W. B. Choi’s group. First we report a Raman spectroscopy study of graphene on copper substrate at high pressures. Diamond anvil cell (DAC) was used to generate pressure. In situ Raman spectra were collected at pressures up to 10 GPa. The results indicate that the G band of graphene shifts with pressure significantly (about 5 cm-1/GPa) whereas the 2D band changes very little. The plasma treated samples were loaded into DAC. Raman spectrum was captured. Parts of the spectrum which were not related to the grapheme peak position were eliminated. The background was reduced. Peaks were found and fitted using FITYK software and the shift of each peak compared to its last position was observed when the pressure was increased. Next we studied plasma treated graphene samples treated with different partial pressure treatments under high pressure and compared them to each other using zirconia anvil cell with the same method

Graphene under hydrostatic pressure

In-situ high pressure Raman spectroscopy is used to study monolayer, bilayer and few-layer graphene samples supported on silicon in a diamond anvil cell to 3.5 GPa. The results show that monolayer graphene adheres to the silicon substrate under compressive stress. A clear trend in this behaviour as a function of graphene sample thickness is observed. We also study unsupported graphene samples in a diamond anvil cell to 8 GPa, and show that the properties of graphene under compression are intrinsically similar to graphite. Our results demonstrate the differing effects of uniaxial and biaxial strain on the electronic bandstructure.Comment: Accepted in Physical Review B with minor change

Hidden area and mechanical nonlinearities in freestanding graphene

We investigated the effect of out-of-plane crumpling on the mechanical response of graphene membranes. In our experiments, stress was applied to graphene membranes using pressurized gas while the strain state was monitored through two complementary techniques: interferometric profilometry and Raman spectroscopy. By comparing the data obtained through these two techniques, we determined the geometric hidden area which quantifies the crumpling strength. While the devices with hidden area $\sim0~\%$ obeyed linear mechanics with biaxial stiffness $428\pm10$ N/m, specimens with hidden area in the range $0.5-1.0~\%$ were found to obey an anomalous Hooke's law with an exponent $\sim0.1$

Raman spectroscopic determination of the length, strength, compressibility, Debye temperature, elasticity, and force constant of the C-C bond in graphene

From the perspective of bond relaxation and vibration, we have reconciled the Raman shifts of graphene under the stimuli of the number-of-layer, uni-axial-strain, pressure, and temperature in terms of the response of the length and strength of the representative bond of the entire specimen to the applied stimuli. Theoretical unification of the measurements clarifies that: (i) the opposite trends of Raman shifts due to number-of-layer reduction indicate that the G-peak shift is dominated by the vibration of a pair of atoms while the D- and the 2D-peak shifts involves z-neighbor of a specific atom; (ii) the tensile strain-induced phonon softening and phonon-band splitting arise from the asymmetric response of the C3v bond geometry to the C2v uni-axial bond elongation; (iii) the thermal-softening of the phonons originates from bond expansion and weakening; and (iv) the pressure- stiffening of the phonons results from bond compression and work hardening. Reproduction of the measurements has led to quantitative information about the referential frequencies from which the Raman frequencies shift, the length, energy, force constant, Debye temperature, compressibility, elastic modulus of the C-C bond in graphene, which is of instrumental importance to the understanding of the unusual behavior of graphene

Direct exfoliation and dispersion of two-dimensional materials in pure water via temperature control

The high-volume synthesis of two-dimensional (2D) materials in the form of platelets is desirable for various applications. While water is considered an ideal dispersion medium, due to its abundance and low cost, the hydrophobicity of platelet surfaces has prohibited its widespread use. Here we exfoliate 2D materials directly in pure water without using any chemicals or surfactants. In order to exfoliate and disperse the materials in water, we elevate the temperature of the sonication bath, and introduce energy via the dissipation of sonic waves. Storage stability greater than one month is achieved through the maintenance of high temperatures, and through atomic and molecular level simulations, we further discover that good solubility in water is maintained due to the presence of platelet surface charges as a result of edge functionalization or intrinsic polarity. Finally, we demonstrate inkjet printing on hard and flexible substrates as a potential application of water-dispersed 2D materials.close1