Colloidal TiO2 nanocrystals with engineered defectivity and optical properties.

Partially reduced forms of titanium dioxide (sometimes called "black" titania) have attracted widespread interest as promising photocatalysts of oxidation due to their absorption in the visible region. The main approaches to produce it rely on postprocessing at high temperatures (up to 800 °C) and high pressures (up to 40 bar) or on highly reactive precursors (e.g., TiH2), and yield powders with poorly controlled sizes, shapes, defect concentrations and distributions. We describe an approach for the one-step synthesis of TiO2 colloidal nanocrystals at atmospheric pressure and temperatures as low as 280 °C. The temperature of the reaction allows the density of oxygen vacancies to be controlled by nearly two orders of magnitude independently of their size, shape, or colloidal stability. This synthetic pathway appears to produce vacancies that are homogeneously distributed in the nanocrystals, rather than being concentrated in an amorphous shell. As a result, the defects are protected from oxidation and result in stable optical properties in oxidizing environments.

Moiré Modulation of Van Der Waals Potential in Twisted Hexagonal Boron Nitride.

When a twist angle is applied between two layered materials (LMs), the registry of the layers and the associated change in their functional properties are spatially modulated, and a moiré superlattice arises. Several works explored the optical, electric, and electromechanical moiré-dependent properties of such twisted LMs but, to the best of our knowledge, no direct visualization and quantification of van der Waals (vdW) interlayer interactions has been presented, so far. Here, we use tapping mode atomic force microscopy phase-imaging to probe the spatial modulation of the vdW potential in twisted hexagonal boron nitride. We find a moiré superlattice in the phase channel only when noncontact (long-range) forces are probed, revealing the modulation of the vdW potential at the sample surface, following AB and BA stacking domains. The creation of scalable electrostatic domains, modulating the vdW potential at the interface with the environment by means of layer twisting, could be used for local adhesion engineering and surface functionalization by affecting the deposition of molecules or nanoparticles.

Electrically Tunable Nonequilibrium Optical Response of Graphene.

The ability to tune the optical response of a material via electrostatic gating is crucial for optoelectronic applications, such as electro-optic modulators, saturable absorbers, optical limiters, photodetectors, and transparent electrodes. The band structure of single layer graphene (SLG), with zero-gap, linearly dispersive conduction and valence bands, enables an easy control of the Fermi energy, EF, and of the threshold for interband optical absorption. Here, we report the tunability of the SLG nonequilibrium optical response in the near-infrared (1000-1700 nm/0.729-1.240 eV), exploring a range of EF from -650 to 250 meV by ionic liquid gating. As EF increases from the Dirac point to the threshold for Pauli blocking of interband absorption, we observe a slow-down of the photobleaching relaxation dynamics, which we attribute to the quenching of optical phonon emission from photoexcited charge carriers. For EF exceeding the Pauli blocking threshold, photobleaching eventually turns into photoinduced absorption, because the hot electrons' excitation increases the SLG absorption. The ability to control both recovery time and sign of the nonequilibrium optical response by electrostatic gating makes SLG ideal for tunable saturable absorbers with controlled dynamics.

Chip-Scalable, Room-Temperature, Zero-Bias, Graphene-Based Terahertz Detectors with Nanosecond Response Time.

The scalable synthesis and transfer of large-area graphene underpins the development of nanoscale photonic devices ideal for new applications in a variety of fields, ranging from biotechnology, to wearable sensors for healthcare and motion detection, to quantum transport, communications, and metrology. We report room-temperature zero-bias thermoelectric photodetectors, based on single- and polycrystal graphene grown by chemical vapor deposition (CVD), tunable over the whole terahertz range (0.1-10 THz) by selecting the resonance of an on-chip patterned nanoantenna. Efficient light detection with noise equivalent powers <1 nWHz-1/2 and response time ∼5 ns at room temperature are demonstrated. This combination of specifications is orders of magnitude better than any previous CVD graphene photoreceiver operating in the sub-THz and THz range. These state-of-the-art performances and the possibility of upscaling to multipixel architectures on complementary metal-oxide-semiconductor platforms are the starting points for the realization of cost-effective THz cameras in a frequency range still not covered by commercially available microbolometer arrays.

Nanoscale Design of the Local Density of Optical States.

We propose a design concept for tailoring the local density of optical states (LDOS) in dielectric nanostructures, based on the phase distribution of the scattered optical fields induced by point-like emitters. First we demonstrate that the LDOS can be expressed in terms of a coherent summation of constructive and destructive contributions. By using an iterative approach, dielectric nanostructures can be designed to effectively remove the destructive terms. In this way, dielectric Mie resonators, featuring low LDOS for electric dipoles, can be reshaped to enable enhancements of 3 orders of magnitude. To demonstrate the generality of the method, we also design nanocavities that enhance the radiated power of a circular dipole, a quadrupole, and an arbitrary collection of coherent dipoles. Our concept provides a powerful tool for high-performance dielectric resonators and affords fundamental insights into light-matter coupling at the nanoscale.

Intervalley scattering by acoustic phonons in two-dimensional MoS2 revealed by double-resonance Raman spectroscopy.

Double-resonance Raman scattering is a sensitive probe to study the electron-phonon scattering pathways in crystals. For semiconducting two-dimensional transition-metal dichalcogenides, the double-resonance Raman process involves different valleys and phonons in the Brillouin zone, and it has not yet been fully understood. Here we present a multiple energy excitation Raman study in conjunction with density functional theory calculations that unveil the double-resonance Raman scattering process in monolayer and bulk MoS2. Results show that the frequency of some Raman features shifts when changing the excitation energy, and first-principle simulations confirm that such bands arise from distinct acoustic phonons, connecting different valley states. The double-resonance Raman process is affected by the indirect-to-direct bandgap transition, and a comparison of results in monolayer and bulk allows the assignment of each Raman feature near the M or K points of the Brillouin zone. Our work highlights the underlying physics of intervalley scattering of electrons by acoustic phonons, which is essential for valley depolarization in MoS2.

Nanoscale mapping of excitonic processes in single-layer MoS2 using tip-enhanced photoluminescence microscopy.

In two-dimensional (2D) semiconductors, photoluminescence originating from recombination processes involving neutral electron-hole pairs (excitons) and charged complexes (trions) is strongly affected by the localized charge transfer due to inhomogeneous interactions with the local environment and surface defects. Herein, we demonstrate the first nanoscale mapping of excitons and trions in single-layer MoS2 using the full spectral information obtained via tip-enhanced photoluminescence (TEPL) microscopy along with tip-enhanced Raman spectroscopy (TERS) imaging of a 2D flake. Finally, we show the mapping of the PL quenching centre in single-layer MoS2 with an unprecedented spatial resolution of 20 nm. In addition, our research shows that unlike in aperture-scanning near field microscopy, preferential exciton emission mapping at the nanoscale using TEPL and Raman mapping using TERS can be obtained simultaneously using this method that can be used to correlate the structural and excitonic properties.

Probing individual point defects in graphene via near-field Raman scattering.

The Raman scattering D-peak in graphene is spatially localised in close proximity to defects. Here, we demonstrate the capability of tip-enhanced Raman spectroscopy (TERS) to probe individual point defects, even for a graphene layer with an extremely low defect density. This is of practical interest for future graphene electronic devices. The measured TERS spectra enable a direct determination of the average inter-defect distance within the graphene sheet. Analysis of the TERS enhancement factor of the graphene Raman peaks highlights the preferential enhancement and symmetry-dependent selectivity of the D-peak intensity caused by zero-dimensional Raman scatterers.