Picosecond energy transfer in a transition metal dichalcogenide-graphene heterostructure revealed by transient Raman spectroscopy.

Intense light­matter interactions and unique structural and electrical properties make van der Waals heterostructures composed by graphene (Gr) and monolayer transition metal dichalcogenides (TMD) promising building blocks for tunneling transistors and flexible electronics, as well as optoelectronic devices, including photodetectors, photovoltaics, and quantum light emitting devices (QLEDs), bright and narrow-line emitters using minimal amounts of active absorber material. The performance of such devices is critically ruled by interlayer interactions which are still poorly understood in many respects. Specifically, two classes of coupling mechanisms have been proposed, charge transfer (CT) and energy transfer (ET), but their relative efficiency and the underlying physics are open questions. Here, building on a time-resolved Raman scattering experiment, we determine the electronic temperature profile of Gr in response to TMD photoexcitation, tracking the picosecond dynamics of the G and 2D Raman bands. Compelling evidence for a dominant role of the ET process accomplished within a characteristic time of ∼4 ps is provided. Our results suggest the existence of an intermediate process between the observed picosecond ET and the generation of a net charge underlying the slower electric signals detected in optoelectronic applications.

Tip-induced excitonic luminescence nanoscopy of an atomically resolved van der Waals heterostructure.

The electronic and optical properties of van der Waals heterostructures are strongly influenced by the structuration and homogeneity of their nano- and atomic-scale environments. Unravelling this intimate structure-property relationship is a key challenge that requires methods capable of addressing the light-matter interactions in van der Waals materials with ultimate spatial resolution. Here we use a low-temperature scanning tunnelling microscope to probe-with atomic-scale resolution-the excitonic luminescence of a van der Waals heterostructure, made of a transition metal dichalcogenide monolayer stacked onto a few-layer graphene flake supported by a Au(111) substrate. Sharp emission lines arising from neutral, charged and localized excitons are reported. Their intensities and emission energies vary as a function of the nanoscale topography of the van der Waals heterostructure, explaining the variability of the emission properties observed with diffraction-limited approaches. Our work paves the way towards understanding and controlling optoelectronic phenomena in moiré superlattices with atomic-scale resolution.

Tip-Induced and Electrical Control of the Photoluminescence Yield of Monolayer WS2.

The photoluminescence (PL) of monolayer tungsten disulfide (WS2) is locally and electrically controlled using the nonplasmonic tip and tunneling current of a scanning tunneling microscope (STM). The spatial and spectral distribution of the emitted light is determined using an optical microscope. When the STM tip is engaged, short-range PL quenching due to near-field electromagnetic effects is present, independent of the sign and value of the bias voltage applied to the tip-sample tunneling junction. In addition, a bias-voltage-dependent long-range PL quenching is measured when the sample is positively biased. We explain these observations by considering the native n-doping of monolayer WS2 and the charge carrier density gradients induced by electron tunneling in micrometer-scale areas around the tip position. The combination of wide-field PL microscopy and charge carrier injection using an STM opens up new ways to explore the interplay between excitons and charge carriers in two-dimensional semiconductors.

Scanning Tunneling Microscope-Induced Excitonic Luminescence of a Two-Dimensional Semiconductor.

The long sought-after goal of locally and spectroscopically probing the excitons of two-dimensional (2D) semiconductors is attained using a scanning tunneling microscope (STM). Excitonic luminescence from monolayer molybdenum diselenide (MoSe_{2}) on a transparent conducting substrate is electrically excited in the tunnel junction of an STM under ambient conditions. By comparing the results with photoluminescence measurements, the emission mechanism is identified as the radiative recombination of bright A excitons. STM-induced luminescence is observed at bias voltages as low as those that correspond to the energy of the optical band gap of MoSe_{2}. The proposed excitation mechanism is resonance energy transfer from the tunneling current to the excitons in the semiconductor, i.e., through virtual photon coupling. Additional mechanisms (e.g., charge injection) may come into play at bias voltages that are higher than the electronic band gap. Photon emission quantum efficiencies of up to 10^{-7} photons per electron are obtained, despite the lack of any participating plasmons. Our results demonstrate a new technique for investigating the excitonic and optoelectronic properties of 2D semiconductors and their heterostructures at the nanometer scale.

Quantum Interference Effects in Resonant Raman Spectroscopy of Single- and Triple-Layer MoTe2 from First-Principles.

We present a combined experimental and theoretical study of resonant Raman spectroscopy in single- and triple-layer MoTe2. Raman intensities are computed entirely from first-principles by calculating finite differences of the dielectric susceptibility. In our analysis, we investigate the role of quantum interference effects and the electron-phonon coupling. With this method, we explain the experimentally observed intensity inversion of the A1' vibrational modes in triple-layer MoTe2 with increasing laser photon energy. Finally, we show that a quantitative comparison with experimental data requires the proper inclusion of excitonic effects.

Vibronic Spectroscopy with Submolecular Resolution from STM-Induced Electroluminescence.

A scanning tunneling microscope is used to generate the electroluminescence of phthalocyanine molecules deposited on NaCl/Ag(111). Photon spectra reveal an intense emission line at ≈1.9 eV that corresponds to the fluorescence of the molecules, and a series of weaker redshifted lines. Based on a comparison with Raman spectra acquired on macroscopic molecular crystals, these spectroscopic features can be associated with the vibrational modes of the molecules and provide a detailed chemical fingerprint of the probed species. Maps of the vibronic features reveal submolecularly resolved structures whose patterns are related to the symmetry of the probed vibrational modes.

Unified Description of the Optical Phonon Modes in N-Layer MoTe2.

N-layer transition metal dichalcogenides provide a unique platform to investigate the evolution of the physical properties between the bulk (three-dimensional) and monolayer (quasi-two-dimensional) limits. Here, using high-resolution micro-Raman spectroscopy, we report a unified experimental description of the Γ-point optical phonons in N-layer 2H-molybdenum ditelluride (MoTe2). We observe series of N-dependent low-frequency interlayer shear and breathing modes (below 40 cm(-1), denoted LSM and LBM) and well-defined Davydov splittings of the mid-frequency modes (in the range 100-200 cm(-1), denoted iX and oX), which solely involve displacements of the chalcogen atoms. In contrast, the high-frequency modes (in the range 200-300 cm(-1), denoted iMX and oMX), arising from displacements of both the metal and chalcogen atoms, exhibit considerably reduced splittings. The manifold of phonon modes associated with the in-plane and out-of-plane displacements are quantitatively described by a force constant model, including interactions up to the second nearest neighbor and surface effects as fitting parameters. The splittings for the iX and oX modes observed in N-layer crystals are directly correlated to the corresponding bulk Davydov splittings between the E2u/E1g and B1u/A1g modes, respectively, and provide a measurement of the frequencies of the bulk silent E2u and B1u optical phonon modes. Our analysis could readily be generalized to other layered crystals.

Distance dependence of the energy transfer rate from a single semiconductor nanostructure to graphene.

The near-field Coulomb interaction between a nanoemitter and a graphene monolayer results in strong Förster-type resonant energy transfer and subsequent fluorescence quenching. Here, we investigate the distance dependence of the energy transfer rate from individual, (i) zero-dimensional CdSe/CdS nanocrystals and (ii) two-dimensional CdSe/CdS/ZnS nanoplatelets to a graphene monolayer. For increasing distances d, the energy transfer rate from individual nanocrystals to graphene decays as 1/d(4). In contrast, the distance dependence of the energy transfer rate from a two-dimensional nanoplatelet to graphene deviates from a simple power law but is well described by a theoretical model, which considers a thermal distribution of free excitons in a two-dimensional quantum well. Our results show that accurate distance measurements can be performed at the single particle level using graphene-based molecular rulers and that energy transfer allows probing dimensionality effects at the nanoscale.

Probing electronic excitations in mono- to pentalayer graphene by micro magneto-Raman spectroscopy.

We probe electronic excitations between Landau levels in freestanding N-layer graphene over a broad energy range, with unprecedented spectral and spatial resolution, using micro magneto-Raman scattering spectroscopy. A characteristic evolution of electronic bands in up to five Bernal-stacked graphene layers is evidenced and shown to remarkably follow a simple theoretical approach, based on an effective bilayer model. (N > 3)-layer graphenes appear as appealing candidates in the quest for novel phenomena, particularly in the quantum Hall effect regime. Our work paves the way toward minimally invasive investigations of magneto-excitons in other emerging low-dimensional systems, with a spatial resolution down to 1 µm.

Intrinsic line shape of the Raman 2D-mode in freestanding graphene monolayers.

We report a comprehensive study of the two-phonon intervalley (2D) Raman mode in graphene monolayers, motivated by recent reports of asymmetric 2D-mode line shapes in freestanding graphene. For photon energies in the range 1.53-2.71 eV, the 2D-mode Raman response of freestanding samples appears as bimodal, in stark contrast with the Lorentzian approximation that is commonly used for supported monolayers. The transition between the freestanding and supported cases is mimicked by electrostatically doping freestanding graphene at carrier densities above 2 × 10(11) cm(-2). This result quantitatively demonstrates that low levels of charging can obscure the intrinsically bimodal 2D-mode line shape of monolayer graphene. In pristine freestanding graphene, we observe a broadening of the 2D-mode feature with decreasing photon energy that cannot be rationalized using a simple one-dimensional model based on resonant inner and outer processes. This indicates that phonon wavevectors away from the high-symmetry lines of the Brillouin zone must contribute to the 2D-mode, so that a full two-dimensional calculation is required to properly describe multiphonon-resonant Raman processes.

Submolecular-scale control of phototautomerization.

Optically activated reactions initiate biological processes such as photosynthesis or vision, but can also control polymerization, catalysis or energy conversion. Methods relying on the manipulation of light at macroscopic and mesoscopic scales are used to control on-surface photochemistry, but do not offer atomic-scale control. Here we take advantage of the confinement of the electromagnetic field at the apex of a scanning tunnelling microscope tip to drive the phototautomerization of a free-base phthalocyanine with submolecular precision. We can control the reaction rate and the relative tautomer population through a change in the laser excitation wavelength or through the tip position. Atomically resolved tip-enhanced photoluminescence spectroscopy and hyperspectral mapping unravel an excited-state mediated process, which is quantitatively supported by a comprehensive theoretical model combining ab initio calculations with a parametric open-quantum-system approach. Our experimental strategy may allow insights in other photochemical reactions and proof useful to control complex on-surface reactions.

Large-Scale Statistical Analysis of Defect Emission in hBN: Revealing Spectral Families and Influence of Flake Morphology.

Quantum emitters in two-dimensional layered hexagonal boron nitride are quickly emerging as a highly promising platform for next-generation quantum technologies. However, the precise identification and control of defects are key parameters to achieve the next step in their development. We conducted a comprehensive study by analyzing over 10,000 photoluminescence emission lines from liquid exfoliated hBN nanoflake samples, revealing 11 narrow sets of defect families within the 1.6 to 2.2 eV energy range. This challenges hypotheses of a random energy distribution. We also reported averaged defect parameters, including emission line widths, spatial density, phonon side bands, and Franck-Condon-related factors. These findings provide valuable insights into deciphering the microscopic origin of emitters in hBN hosts. We also explored the influence of the hBN host morphology on defect family formation, demonstrating its crucial impact. By tuning the flake size and arrangement, we achieve selective control of defect types while maintaining high spatial density. This offers a scalable approach to defect emission control, diverging from costly engineering methods. It emphasizes the significance of the morphological aspects of hBN hosts for gaining insights into defect origins and expanding their spectral control.

Epitaxy of MgO magnetic tunnel barriers on epitaxial graphene.

Epitaxial growth of electrodes and tunnel barriers on graphene is one of the main technological bottlenecks for graphene spintronics. In this paper, we demonstrate that MgO(111) epitaxial tunnel barriers, one of the prime candidates for spintronic application, can be grown by molecular beam epitaxy on epitaxial graphene on SiC(0001). Ferromagnetic metals (Fe, Co, Fe20Ni80) were epitaxially grown on top of the MgO barrier, thus leading to monocrystalline electrodes on graphene. Structural and magnetic characterizations were performed on these ferromagnetic metals after annealing and dewetting: they form clusters with a 100 nm typical lateral width, which are mostly magnetic monodomains in the case of Fe. This epitaxial stack opens the way to graphene spintronic devices taking benefits from a coherent tunnelling current through the epitaxial MgO/graphene stack.

Low bias electron scattering in structure-identified single wall carbon nanotubes: role of substrate polar phonons.

We have performed temperature-dependent electrical transport measurements on known structure single wall carbon nanotubes at low bias. The experiments show a superlinear increase in nanotube resistivity with temperature, which is in contradiction with the linear dependence expected from nanotube acoustic-phonon scattering. The measured electron mean free path is also much lower than expected, especially at medium to high temperatures (>100 K). A theoretical model that includes scattering due to surface polar phonon modes of the substrates reproduces the experiments very well. The role of surface phonons is further confirmed by resistivity measurements of nanotubes on aluminum nitride.

All-optical trion generation in single-walled carbon nanotubes.

We present evidence of all-optical trion generation and emission in pristine single-walled carbon nanotubes (SWCNTs). Luminescence spectra, recorded on individual SWCNTs over a large cw excitation intensity range, show trion emission peaks redshifted with respect to the bright exciton peak. Clear chirality dependence is observed for 22 separate SWCNT species, allowing for determination of electron-hole exchange interaction and trion binding energy contributions. Luminescence data together with ultrafast pump-probe experiments on chirality-sorted bulk samples suggest that exciton-exciton annihilation processes generate dissociated carriers that allow for trion creation upon a subsequent photon absorption event.

Atmospheric oxygen binding and hole doping in deformed graphene on a SiO2 substrate.

Using micro-Raman spectroscopy and scanning tunneling microscopy, we study the relationship between structural distortion and electrical hole doping of graphene on a silicon dioxide substrate. The observed upshift of the Raman G band represents charge doping and not compressive strain. Two independent factors control the doping: (1) the degree of graphene coupling to the substrate and (2) exposure to oxygen and moisture. Thermal annealing induces a pronounced structural distortion due to close coupling to SiO2 and activates the ability of diatomic oxygen to accept charge from graphene. Gas flow experiments show that dry oxygen reversibly dopes graphene; doping becomes stronger and more irreversible in the presence of moisture and over long periods of time. We propose that oxygen molecular anions are stabilized by water solvation and electrostatic binding to the silicon dioxide surface.

Electron and optical phonon temperatures in electrically biased graphene.

We examine the intrinsic energy dissipation steps in electrically biased graphene channels. By combining in-situ measurements of the spontaneous optical emission with a Raman spectroscopy study of the graphene sample under conditions of current flow, we obtain independent information on the energy distribution of the electrons and phonons. The electrons and holes contributing to light emission are found to obey a thermal distribution, with temperatures in excess of 1500 K in the regime of current saturation. The zone-center optical phonons are also highly excited and are found to be in equilibrium with the electrons. For a given optical phonon temperature, the anharmonic downshift of the Raman G mode is smaller than expected under equilibrium conditions, suggesting that the electrons and high-energy optical phonons are not fully equilibrated with all of the phonon modes.

Dynamically-enhanced strain in atomically thin resonators.

Graphene and related two-dimensional (2D) materials associate remarkable mechanical, electronic, optical and phononic properties. As such, 2D materials are promising for hybrid systems that couple their elementary excitations (excitons, phonons) to their macroscopic mechanical modes. These built-in systems may yield enhanced strain-mediated coupling compared to bulkier architectures, e.g., comprising a single quantum emitter coupled to a nano-mechanical resonator. Here, using micro-Raman spectroscopy on pristine monolayer graphene drums, we demonstrate that the macroscopic flexural vibrations of graphene induce dynamical optical phonon softening. This softening is an unambiguous fingerprint of dynamically-induced tensile strain that reaches values up to ≈4 × 10-4 under strong non-linear driving. Such non-linearly enhanced strain exceeds the values predicted for harmonic vibrations with the same root mean square (RMS) amplitude by more than one order of magnitude. Our work holds promise for dynamical strain engineering and dynamical strain-mediated control of light-matter interactions in 2D materials and related heterostructures.

Filtering the photoluminescence spectra of atomically thin semiconductors with graphene.

Atomically thin semiconductors made from transition metal dichalcogenides (TMDs) are model systems for investigations of strong light-matter interactions and applications in nanophotonics, optoelectronics and valleytronics. However, the photoluminescence spectra of TMD monolayers display a large number of features that are particularly challenging to decipher. On a practical level, monochromatic TMD-based emitters would be beneficial for low-dimensional devices, but this challenge is yet to be resolved. Here, we show that graphene, directly stacked onto TMD monolayers, enables single and narrow-line photoluminescence arising solely from TMD neutral excitons. This filtering effect stems from complete neutralization of the TMD by graphene, combined with selective non-radiative transfer of long-lived excitonic species to graphene. Our approach is applied to four tungsten- and molybdenum-based TMDs and establishes TMD/graphene heterostructures as a unique set of optoelectronic building blocks that are suitable for electroluminescent systems emitting visible and near-infrared photons at near THz rate with linewidths approaching the homogeneous limit.

Reconfigurable 2D/0D p-n Graphene/HgTe Nanocrystal Heterostructure for Infrared Detection.

Nanocrystals are promising building blocks for the development of low-cost infrared optoelectronics. Gating a nanocrystal film in a phototransistor geometry is commonly proposed as a strategy to tune the signal-to-noise ratio by carefully controlling the carrier density within the semiconductor. However, the performance improvement has so far been quite marginal. With metallic electrodes, the gate dependence of the photocurrent follows the gate-induced change of the dark current. Graphene presents key advantages: (i) infrared transparency that allows back-side illumination, (ii) vertical electric field transparency, and (iii) carrier selectivity under gate bias. Here, we investigate a configuration of 2D/0D infrared photodetectors taking advantage of a high capacitance ionic glass gate, large-scale graphene electrodes, and a HgTe nanocrystals layer of high carrier mobility. The introduction of graphene electrodes combined with ionic glass enables one to reconfigure selectively the HgTe nanocrystals and the graphene electrodes between electron-doped (n) and hole-doped (p) states. We unveil that this functionality enables the design a 2D/0D p-n junction that expands throughout the device, with a built-in electric field that assists charge dissociation. We demonstrate that, in this specific configuration, the signal-to-noise ratio for infrared photodetection can be enhanced by 2 orders of magnitude, and that photovoltaic operation can be achieved. The detectivity now reaches 109 Jones, whereas the device only absorbs 8% of the incident light. Additionally, the time response of the device is fast (<10 µs), which strongly contrasts with the slow response commonly observed for 2D/0D mixed-dimensional heterostructures, where larger photoconduction gains come at the cost of slower response.