In monolayer graphene, substitutional doping during growth can be used to alter its electronic properties. We used scanning tunneling microscopy, Raman spectroscopy, x-ray spectroscopy, and first principles calculations to characterize individual nitrogen dopants in monolayer graphene grown on a copper substrate. Individual nitrogen atoms were incorporated as graphitic dopants, and a fraction of the extra electron on each nitrogen atom was delocalized into the graphene lattice. The electronic structure of nitrogen-doped graphene was strongly modified only within a few lattice spacings of the site of the nitrogen dopant. These findings show that chemical doping is a promising route to achieving high-quality graphene films with a large carrier concentration.
Robust methods to tune the unique electronic properties of graphene by chemical modification are in great demand due to the potential of the two dimensional material to impact a range of device applications. Here we show that carbon and nitrogen core-level resonant X-ray spectroscopy is a sensitive probe of chemical bonding and electronic structure of chemical dopants introduced in single-sheet graphene films. In conjunction with density functional theory based calculations, we are able to obtain a detailed picture of bond types and electronic structure in graphene doped with nitrogen at the sub-percent level. We show that different N-bond types, including graphitic, pyridinic, and nitrilic, can exist in a single, dilutely N-doped graphene sheet. We show that these various bond types have profoundly different effects on the carrier concentration, indicating that control over the dopant bond type is a crucial requirement in advancing graphene electronics.
In nanomaterials, optical anisotropies reveal a fundamental relationship between structural and optical properties. Directional optical properties can be exploited to enhance the performance of optoelectronic devices, optomechanical actuators and metamaterials. In layered materials, optical anisotropies may result from in-plane and out-of-plane dipoles associated with intra- and interlayer excitations, respectively. Here, we resolve the orientation of luminescent excitons and isolate photoluminescence signatures arising from distinct intra- and interlayer optical transitions. Combining analytical calculations with energy- and momentum-resolved spectroscopy, we distinguish between in-plane and out-of-plane oriented excitons in materials with weak or strong interlayer coupling-MoS₂ and 3,4,9,10-perylene tetracarboxylic dianhydride (PTCDA), respectively. We demonstrate that photoluminescence from MoS₂ mono-, bi- and trilayers originates solely from in-plane excitons, whereas PTCDA supports distinct in-plane and out-of-plane exciton species with different spectra, dipole strengths and temporal dynamics. The insights provided by this work are important for understanding fundamental excitonic properties in nanomaterials and designing optical systems that efficiently excite and collect light from exciton species with different orientations.
Here we present a review of x-ray absorption spectroscopy and x-ray Raman scattering with the perspective to understand the spectra of water including changes with temperature, mass of the water molecule and presence of monovalent ions. The different detection schemes are discussed and it is concluded that transmission x-ray absorption measurements, using a small area where the thickness is uniform, and x-ray Raman scattering give the most reliable spectra. Different model systems are discussed such as the surface and bulk of ice and various adsorbed monolayer structures on metal surfaces.
We use scanning tunneling microscopy and X-ray spectroscopy to characterize the atomic and electronic structure of boron-doped and nitrogen-doped graphene created by chemical vapor deposition on copper substrates. Microscopic measurements show that boron, like nitrogen, incorporates into the carbon lattice primarily in the graphitic form and contributes ~0.5 carriers into the graphene sheet per dopant. Density functional theory calculations indicate that boron dopants interact strongly with the underlying copper substrate while nitrogen dopants do not. The local bonding differences between graphitic boron and nitrogen dopants lead to large scale differences in dopant distribution. The distribution of dopants is observed to be completely random in the case of boron, while nitrogen displays strong sublattice clustering. Structurally, nitrogen-doped graphene is relatively defect-free while boron-doped graphene films show a large number of Stone-Wales defects. These defects create local electronic resonances and cause electronic scattering, but do not electronically dope the graphene film.
We report different wetting properties of Cu(110) and Cu(111) at near-ambient conditions using in situ photoemission spectroscopy. At near-ambient conditions of pressure (1 Torr) and temperature (295 K), the Cu(110) surface is covered with a mixed OH and H2O layer, whereas the Cu(111) surface remains clean and adsorbate-free. We show that wetting is controlled by the presence of OH groups on the surface, acting as anchors for water adsorption. Hydroxylation of the Cu(110) surface is facilitated by a lower activation barrier for water dissociation compared to Cu(111).
Epitaxial van der Waals (vdW) heterostructures of organic and layered materials are demonstrated to create high-performance organic electronic devices. High-quality rubrene films with large single-crystalline domains are grown on h-BN dielectric layers via vdW epitaxy. In addition, high carrier mobility comparable to free-standing single-crystal counterparts is achieved by forming interfacial electrical contacts with graphene electrodes.
MoTe2 is an exfoliable transition metal dichalcogenide (TMD) which crystallizes in three symmetries; the semiconducting trigonal-prismatic 2H−phase, the semimetallic 1T ′ monoclinic phase, and the semimetallic orthorhombic T d structure 1-4 . The 2H−phase displays a band gap of ∼ 1 eV 5 making it appealing for flexible and transparent optoelectronics. The T d−phase is predicted to possess unique topological properties 6-9 which might lead to topologically protected non-dissipative transport channels 9 . Recently, it was argued that it is possible to locally induce phasetransformations in TMDs 3,10,11,14 , through chemical doping 12 , local heating 13 , or electric-field 14,15 to achieve ohmic contacts or to induce useful functionalities such as electronic phase-change memory elements 11 . The combination of semiconducting and topological elements based upon the same compound, might produce a new generation of high performance, low dissipation optoelectronic elements. Here, we show that it is possible to engineer the phases of MoTe2 through W substitution by unveiling the phase-diagram of the Mo1−xWxTe2 solid solution which displays a semiconducting to semimetallic transition as a function of x. We find that only ∼ 8 % of W stabilizes the T d−phase at room temperature. Photoemission spectroscopy, indicates that this phase possesses a Fermi surface akin to that of WTe2 16 .The properties of semiconducting and of semimetallic MoTe 2 are of fundamental interest in their own right, but are also for their potential technological relevance. In the mono-or few-layer limit it is a direct-gap semiconductor, while the bulk has an indirect bandgap 5,17,18 of ∼ 1 eV. The size of the gap is similar to that of Si, making 2H−MoTe 2 particularly appealing for both purely electronic devices 19,20 and optoelectronic applications 21 . Moreover, the existence of different phases opens up the possibility for many novel devices and architectures. For example, controlled conversion of the 1T ′ −MoTe 2 phase to the 2H−phase, as recently reported 22 , could
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