Linear optical methods of determining the chirality of organic and inorganic materials have relied on weak chiral optical (chiroptical) effects. Nonlinear chiroptical characterization holds the potential of much greater sensitivity and smaller interaction volumes. However, suitable materials on which to perform measurements have been lacking for decades. Here, we present the first nonlinear chiroptical characterization of crystallographic chirality in gold helicoids (≈150 nm size) and core/shell helicoids with the newly discovered hyper-Rayleigh scattering optical activity (HRS OA) technique. The observed chiroptical signal is, on average, originating from between ≈0.05 and ≈0.13 helicoids, i.e., less than a single nanoparticle. The measured HRS OA ellipticities reach ≈3°, for a concentration ≈10 9 times smaller than that of chiral molecules with similar nonlinear chiroptical response. These huge values indicate that the helicoids are excellent candidates for future nonlinear chiroptical materials and applications.

We demonstrate a versatile, catalyst free chemical vapor deposition process on insulating substrates capable of producing in one single stream one-dimensional (1D) WO3–x suboxides leading to a wide range of substrate-supported 2H-WS2 polymorphs: a tunable class of out-of-plane (of the substrate) nanophases, with 1D nanotubes and a pure WS2, two-dimensional (2D) nanomesh (defined as a network of webbed, micron-size, few-layer 2D sheets) at its extremes; and in-plane (parallel to the substrate) mono- and few-layer 2D domains. This entails a two-stage approach in which the 2WO3 + 7S → 2WS2 + 3SO2 reaction is intentionally decoupled. First, various morphologies of nanowires or nanorods of high stoichiometry, WO2.92/WO2.9 suboxides (belonging to the class of Magnéli phases) were formed, followed by their sulfurization to undergo reduction to the aforementioned WS2 polymorphs. The continuous transition of WS2 from nanotubes to the out-of-plane 2D nanomesh, via intermediary, mixed 1D-2D phases, delivers tunable functional properties, for example, linear and nonlinear optical properties, such as reflectivity (linked to optical excitations in the material), and second harmonic generation (SHG) and onset of saturable absorption. The SHG effect is very strong across the entire tunable class of WS2 nanomaterials, weakest in nanotubes, and strongest in the 2D nanomesh. Furthermore, a mechanism via suboxide (WO3–x ) intermediate as a possible path to 2D domain growth is demonstrated. 2D, in-plane WS2 domains grow via “self-seeding and feeding” where short WO2.92/WO2.9 nanorods provide both the nucleation sites and the precursor feedstock. Understanding the reaction path (here, in the W–O–S space) is an emerging approach toward controlling the nucleation, growth, and morphology of 2D domains and films of transition-metal dichalcogenides.

Photograph of the experimental setup with light diffracting from a racemic nanoarray. The diffracted spectra change depending on the direction of circularly polarized illumination.

The cover image represents laser light illuminating a densely‐spaced, randomly‐arranged, 3D‐network of a WS2 polymorph (“nanomesh”), where 2D sheets intersect and twist on top of each other, modifying the energy landscape of the material, as presented by Ventsislav K. Valev and co‐workers in article number 2100117. The multiphoton emission is dominated by large second harmonic generation (SHG) that is doubly resonant at the broad C spectral feature of the transition metal dichalcogenide.

Although transition metal dichalcogenides (TMDs, e.g., WS2, WSe2, MoS2, MoSe2) have emerged as highly promising 2D materials for nonlinear optics, they are limited by intrinsically small light‐matter interaction length and (typically) flat‐lying geometries. The first hyperspectral multiphoton analysis of a tridimensional webbed network of densely‐packed stacks (of 1–5 layers) of twisted and/or fused 2D nanosheets of WS2, referred to as “nanomesh”, is presented here. The optical second harmonic generation (SHG) is mapped across the three characteristic spectral features (A, B, and C) and two‐photon luminescence and third harmonic generation signatures are established. Compared to flat‐lying WS2 layers, the nanomesh is highly efficient, broadband, and robust against degradation (with main enhancement originating from the C feature, spreading from 850 to 1100 nm), and scalable in terms of growth. The origin of these spectral differences is assigned to hotspots, whose location changes depending on the wavelength of illumination. The main SHG enhancements result from double resonances in an energy landscape modified by in‐built defects (e.g., vacancies and their passivated variants, or grain boundaries) that induce intra‐bandgap energy levels. These characteristics establish the nanomesh as a prime candidate for integration into quantum optical technologies, such as miniaturized devices on chip.