Monitoring reservoir response to earthquakes and fluid extraction, Salton Sea geothermal field, California.

Continuous monitoring of in situ reservoir responses to stress transients provides insights into the evolution of geothermal reservoirs. By exploiting the stress dependence of seismic velocity changes, we investigate the temporal evolution of the reservoir stress state of the Salton Sea geothermal field (SSGF), California. We find that the SSGF experienced a number of sudden velocity reductions (~0.035 to 0.25%) that are most likely caused by openings of fractures due to dynamic stress transients (as small as 0.08 MPa and up to 0.45 MPa) from local and regional earthquakes. Depths of velocity changes are estimated to be about 0.5 to 1.5 km, similar to the depths of the injection and production wells. We derive an empirical in situ stress sensitivity of seismic velocity changes by relating velocity changes to dynamic stresses. We also observe systematic velocity reductions (0.04 to 0.05%) during earthquake swarms in mid-November 2009 and late-December 2010. On the basis of volumetric static and dynamic stress changes, the expected velocity reductions from the largest earthquakes with magnitude ranging from 3 to 4 in these swarms are less than 0.02%, which suggests that these earthquakes are likely not responsible for the velocity changes observed during the swarms. Instead, we argue that velocity reductions may have been induced by poroelastic opening of fractures due to aseismic deformation. We also observe a long-term velocity increase (~0.04%/year) that is most likely due to poroelastic contraction caused by the geothermal production. Our observations demonstrate that seismic interferometry provides insights into in situ reservoir response to stress changes.

Pressure-Induced Charge Transfer Doping of Monolayer Graphene/MoS2 Heterostructure.

A unique way of achieving controllable, pressure-induced charge transfer doping in the graphene/MoS2 heterostructure is proposed. The charge transfer causes an upward shift in the Dirac point with respect to Fermi level at a rate of 15.7 meV GPa(-1) as a function of applied hydrostatic pressure, leading to heavy p-type doping in graphene. The doping was confirmed by I2D /IG measurements.

Pressure-Modulated Conductivity, Carrier Density, and Mobility of Multilayered Tungsten Disulfide.

Tungsten disulfide (WS2) is a layered transition metal dichalcogenide (TMD) that differs from other two-dimensional (2D) compounds such as graphene due to its unique semiconducting, tunable-band-gap nature. Multilayered WS2 exhibits an indirect band gap Eg of ∼1.3 eV, along with a higher load-bearing ability that is promising for strain-tuning device applications, but the electronic properties of multilayered WS2 at higher strain conditions (i.e., static strain >12%) remain an open question. Here we have studied the structural, electronic, electrical, and vibrational properties of multilayered WS2 at hydrostatic pressures up to ∼35 GPa experimentally in a diamond anvil cell and theoretically using first-principles ab initio calculations. Our results show that WS2 undergoes an isostructural semiconductor-to-metallic (S-M) transition at approximately 22 GPa at 280 K, which arises from the overlap of the highest valence and lowest conduction bands. The S-M transition is caused by increased sulfur-sulfur interactions as the interlayer spacing decreases with applied hydrostatic pressure. The metalization in WS2 can be alternatively interpreted as a 2D to 3D (three-dimensional) phase transition that is associated with a substantial modulation of the charge carrier characteristics including a 6-order decrease in resistivity, a 2-order decrease in mobility, and a 4-order increase in carrier concentration. These distinct pressure-tunable characteristics of the dimensionalized WS2 differentiate it from other TMD compounds such as MoS2 and promise future developments in strain-modulated advanced devices.

Thermal Oxidation of WSe2 Nanosheets Adhered on SiO2/Si Substrates.

Because of the drastically different intralayer versus interlayer bonding strengths, the mechanical, thermal, and electrical properties of two-dimensional (2D) materials are highly anisotropic between the in-plane and out-of-plane directions. The structural anisotropy may also play a role in chemical reactions, such as oxidation, reduction, and etching. Here, the composition, structure, and electrical properties of mechanically exfoliated WSe2 nanosheets on SiO2/Si substrates were studied as a function of the extent of thermal oxidation. A major component of the oxidation, as indicated from optical and Raman data, starts from the nanosheet edges and propagates laterally toward the center. Partial oxidation also occurs in certain areas at the surface of the flakes, which are shown to be highly conductive by microwave impedance microscopy. Using secondary ion mass spectroscopy, we also observed extensive oxidation at the WSe2-SiO2 interface. The combination of multiple microcopy methods can thus provide vital information on the spatial evolution of chemical reactions on 2D materials and the nanoscale electrical properties of the reaction products.

Pressure-dependent optical and vibrational properties of monolayer molybdenum disulfide.

Controlling the band gap by tuning the lattice structure through pressure engineering is a relatively new route for tailoring the optoelectronic properties of two-dimensional (2D) materials. Here, we investigate the electronic structure and lattice vibrational dynamics of the distorted monolayer 1T-MoS2 (1T') and the monolayer 2H-MoS2 via a diamond anvil cell (DAC) and density functional theory (DFT) calculations. The direct optical band gap of the monolayer 2H-MoS2 increases by 11.7% from 1.85 to 2.08 eV, which is the highest reported for a 2D transition metal dichalcogenide (TMD) material. DFT calculations reveal a subsequent decrease in the band gap with eventual metallization of the monolayer 2H-MoS2, an overall complex structure-property relation due to the rich band structure of MoS2. Remarkably, the metastable 1T'-MoS2 metallic state remains invariant with pressure, with the J2, A1g, and E2g modes becoming dominant at high pressures. This substantial reversible tunability of the electronic and vibrational properties of the MoS2 family can be extended to other 2D TMDs. These results present an important advance toward controlling the band structure and optoelectronic properties of monolayer MoS2 via pressure, which has vital implications for enhanced device applications.

Pressure-induced semiconducting to metallic transition in multilayered molybdenum disulphide.

Molybdenum disulphide is a layered transition metal dichalcogenide that has recently raised considerable interest due to its unique semiconducting and opto-electronic properties. Although several theoretical studies have suggested an electronic phase transition in molybdenum disulphide, there has been a lack of experimental evidence. Here we report comprehensive studies on the pressure-dependent electronic, vibrational, optical and structural properties of multilayered molybdenum disulphide up to 35 GPa. Our experimental results reveal a structural lattice distortion followed by an electronic transition from a semiconducting to metallic state at ~19 GPa, which is confirmed by ab initio calculations. The metallization arises from the overlap of the valance and conduction bands owing to sulphur-sulphur interactions as the interlayer spacing reduces. The electronic transition affords modulation of the opto-electronic gain in molybdenum disulphide. This pressure-tuned behaviour can enable the development of novel devices with multiple phenomena involving the strong coupling of the mechanical, electrical and optical properties of layered nanomaterials.