Jingzhi Shang

Pyridinic N doped graphene: synthesis, electronic structure, and electrocatalytic property

Different C–N bonding configurations in nitrogen (N) doped carbon materials have different electronic structures. Carbon materials doped with only one kind of C–N bonding configuration are an excellent platform for studying doping effects on the electronic structure and physical/chemical properties. Here we report synthesis of single layer graphene doped with pure pyridinic N by thermal chemical vapour deposition of hydrogen and ethylene on Cu foils in the presence of ammonia. By adjusting the flow rate of ammonia, the atomic ratio of N and C can be modulated from 0 to 16%. The domain like distribution of N incorporated in graphene was revealed by the imaging of Raman spectroscopy and time-of-flight secondary ion mass spectrometry. The ultraviolet photoemission spectroscopy investigation demonstrated that the pyridinic N efficiently changed the valence band structure of graphene, including the raising of density of π states near the Fermi level and the reduction of work function. Such pyridinic N doping in carbon materials was generally considered to be responsible for their oxygen reduction reaction (ORR) activity. The 2e reduction mechanism of ORR on our CNxgraphene revealed by rotating disk electrode voltammetry indicated that the pyridinic N may not be an effective promoter for ORR activity of carbon materials as previously expected.

Hysteresis of Electronic Transport in Graphene Transistors

Graphene field effect transistors commonly comprise graphene flakes lying on SiO(2) surfaces. The gate-voltage dependent conductance shows hysteresis depending on the gate sweeping rate/range. It is shown here that the transistors exhibit two different kinds of hysteresis in their electrical characteristics. Charge transfer causes a positive shift in the gate voltage of the minimum conductance, while capacitive gating can cause the negative shift of conductance with respect to gate voltage. The positive hysteretic phenomena decay with an increase of the number of layers in graphene flakes. Self-heating in a helium atmosphere significantly removes adsorbates and reduces positive hysteresis. We also observed negative hysteresis in graphene devices at low temperature. It is also found that an ice layer on/under graphene has a much stronger dipole moment than a water layer does. Mobile ions in the electrolyte gate and a polarity switch in the ferroelectric gate could also cause negative hysteresis in graphene transistors. These findings improved our understanding of the electrical response of graphene to its surroundings. The unique sensitivity to environment and related phenomena in graphene deserve further studies on nonvolatile memory, electrostatic detection, and chemically driven applications.

The Origin of Fluorescence from Graphene Oxide

Time-resolved fluorescence measurements of graphene oxide in water show multiexponential decay kinetics ranging from 1 ps to 2 ns. Electron-hole recombination from the bottom of the conduction band and nearby localized states to wide-range valance band is suggested as origin of the fluorescence. Excitation wavelength dependence of the fluorescence was caused by relative intensity changes of few emission species. By introducing the molecular orbital concept, the dominant fluorescence was found to originate from the electronic transitions among/between the non-oxidized carbon regions and the boundary of oxidized carbon atom regions, where all three kinds of functionalized groups C-O, C = O and O = C-OH were participating. In the visible spectral range, the ultrafast fluorescence of graphene oxide was observed for the first time.

Nonblinking, Intense Two-Dimensional Light Emitter: Monolayer WS2 Triangles

Monolayer WS2 (1L-WS2), with a direct band gap, provides an ideal platform to investigate unique properties of two-dimensional semiconductors. In this work, light emission of a 1L-WS2 triangle has been studied by using steady-state, time-resolved, and temperature-dependent photoluminescence (PL) spectroscopy. Two groups of 1L-WS2 triangles have been grown by chemical vapor deposition, which exhibit nonuniform and uniform PL, respectively. Observed nonuniform PL features, i.e., quenching and blue-shift in certain areas, are caused by structural imperfection and n-doping induced by charged defects. Uniform PL is found to be intrinsic, intense, and nonblinking, which are attributed to high crystalline quality. The binding energy of the A-exciton is extracted experimentally, which gives direct evidence for the large excitonic effect in 1L-WS2. These superior photon emission features make 1L-WS2 an appealing material for optoelectronic applications such as novel light-emitting and biosensing devices.

Observation of Excitonic Fine Structure in a 2D Transition-Metal Dichalcogenide Semiconductor

Two-dimensional (2D) semiconductors, such as transition-metal dichalcogenide monolayers (TMD 1Ls), have attracted increasing attention owing to the underlying fundamental physics (e.g., many body effects) and the promising optoelectronic applications such as light-emitting diodes. Though much progress has been made, intrinsic excitonic states of TMD 1Ls are still highly debated in theory, which thirsts for direct experimental determination. Here, we report unconventional emission and excitonic fine structure in 1L WS2 revealed by electrical doping and photoexcitation, which reflects the interplay of exciton, trion, and other excitonic states. Tunable excitonic emission has been realized in a controllable manner via electrical and/or optical injection of charge carriers. Remarkably enough, the superlinear (i.e., quadratic) emission is unambiguously observed which is attributed to biexciton states, indicating the strong Coulomb interactions in such a 2D material. In a nearly neutral 1L WS2, trions and biexcitons possess large binding energies of ∼ 10-15 and 45 meV, respectively. Moreover, our finding of electrically induced robust emission opens up a possibility to boost the luminous efficiency of emerging 1L TMD light emitting diodes.

Chemically Driven Tunable Light Emission of Charged and Neutral Excitons in Monolayer WS2

Monolayer (1L) semiconducting transition metal dichacogenides (TMDs) possess remarkable physical and optical properties, promising for a wide range of applications from nanoelectronics to optoelectronics such as light-emitting and sensing devices. Here we report how the molecular adsorption can modulate the light emission and electrical properties of 1L WS2. The dependences of trion and exciton emission on chemical doping are investigated in 1L WS2 by microphotoluminescence (μPL) measurements, where different responses are observed and simulated theoretically. The total PL is strongly enhanced when electron-withdrawing molecules adsorb on 1L WS2, which is attributed to the increase of the exciton formation due to charge transfer. The electrical transport measurements of a 1L WS2 field effect transistor elucidate the effect of the adsorbates on the conductivity, which give evidence for charge transfer between molecules and 1L WS2. These findings open up many opportunities to manipulate the electrical and optical properties of two-dimensional TMDs, which are particularly important for developing optoelectronic devices for chemical and biochemical sensing applications.

Thermal conductivity determination of suspended mono- and bilayer WS2 by Raman spectroscopy

We report the thermal conductivities of monolayer (1L) and bilayer (2L) WS2 grown by chemical vapor deposition (CVD), which are determined by use of temperature and excitation dependences of E2g1 and A1g Raman modes. The first-order temperature coefficients of E2g1 and A1g modes in both supported and suspended WS2 layers were extracted. The frequency shift of the A1g mode with temperature is larger than that of the E2g1 mode for 1L-WS2, which is attributed to stronger electron-phonon coupling for the A1g mode than that for the E2g1 mode. Moreover, by use of the shift of the phonon mode induced by laser heating, the thermal conductivities at room temperature were estimated to be 32 and 53 W/(m·K) for 1L- and 2L-WS2, respectively. Our results provide fundamental information about the thermal properties of WS2 layers, which is crucial for developing applications of atomically-thin WS2 devices.

Graphene-gold metasurface architectures for ultrasensitive plasmonic biosensing

Graphene-gold metasurface architectures that can provide significant gains in plasmonic detection sensitivity for trace-amount target analytes are reported. Benefiting from extreme phase singularities of reflected light induced by strong plasmon-mediated energy confinements, the metasurface demonstrates a much-improved sensitivity to molecular bindings nearby and achieves an ultralow detection limit of 1 × 10(-18) m for 7.3 kDa 24-mer single-stranded DNA.

Strain-induced direct–indirect bandgap transition and phonon modulation in monolayer WS2

In situ strain photoluminescence (PL) and Raman spectroscopy have been employed to exploit the evolutions of the electronic band structure and lattice vibrational responses of chemical vapor deposition (CVD)-grown monolayer tungsten disulphide (WS2) under uniaxial tensile strain. Observable broadening and appearance of an extra small feature at the longer-wavelength side shoulder of the PL peak occur under 2.5% strain, which could indicate the direct-indirect bandgap transition and is further confirmed by our density-functional-theory calculations. As the strain increases further, the spectral weight of the indirect transition gradually increases. Over the entire strain range, with the increase of the strain, the light emissions corresponding to each optical transition, such as the direct bandgap transition (K-K) and indirect bandgap transition (Γ-K, ≥2.5%), exhibit a monotonous linear redshift. In addition, the binding energy of the indirect transition is found to be larger than that of the direct transition, and the slight lowering of the trion dissociation energy with increasing strain is observed. The strain was used to modulate not only the electronic band structure but also the lattice vibrations. The softening and splitting of the in-plane E’ mode is observed under uniaxial tensile strain, and polarization-dependent Raman spectroscopy confirms the observed zigzag-oriented edge of WS2 grown by CVD in previous studies. These findings enrich our understanding of the strained states of monolayer transition-metal dichalcogenide (TMD) materials and lay a foundation for developing applications exploiting their strain-dependent optical properties, including the strain detection and light-emission modulation of such emerging two-dimensional TMDs.

Modulating the electronic structures of graphene by controllable hydrogenation

The evolution of electronic structures of hydrogenated graphene with different amount of hydrogen (H) coverage was investigated by ultraviolet photoemission spectroscopy and optical absorption spectroscopy. Raman spectroscopy and x-ray photoelectron spectroscopy were used to monitor and evaluate the H coverage. At low H coverage, the sp3 CH bonds embedded within a sp2 C matrix behave as defects in graphene and depress the delocalized π electron system. At high H coverage, two localized π electron states originating from the sp2 C clusters encircled by the sp3 CH matrix appear in the electronic band structures, and an opening of a band gap has been observed.