Probing the Laser Ablation of Black Phosphorus by Raman Spectroscopy.

Laser ablation in conjunction with Raman spectroscopy can be used to attain a controllable reduction of the thickness of exfoliated black phosphorus flakes and simultaneous measurement of the local temperature. However, this approach can be affected by several parameters, such as the thickness-dependent heat dissipation. Optical, thermal, and mechanical effects in the flakes and the substrate can influence the laser ablation and may become a source of artifacts on the measurement of the local temperature. In this work, we carry out a systematic investigation of the laser thinning of black phosphorus flakes on SiO2/Si substrates. The counterintuitive results from Raman thermometry are analyzed and elucidated with the help of numerical solutions of the problem, laying the groundwork for a controlled thinning process of this material.

Stability and universal encapsulation of epitaxial Xenes.

In the realm of two-dimensional material frameworks, single-element graphene-like lattices, known as Xenes, pose several issues concerning their environmental stability, with implications for their use in technology transfer to a device layout. In this Discussion, we scrutinize the chemical reactivity of epitaxial silicene, taken as a case in point, in oxygen-rich environments. The oxidation of silicene is detailed by means of a photoemission spectroscopy study upon carefully dosing molecular oxygen under vacuum and subsequent exposure to ambient conditions, showing different chemical reactivity. We therefore propose a sequential Al2O3 encapsulation of silicene as a solution to face degradation, proving its effectiveness by virtue of the interaction between silicene and a silver substrate. Based on this method, we generalize our encapsulation scheme to a large number of metal-supported Xenes by taking into account the case of epitaxial phosphorene-on-gold.

Thickness determination of anisotropic van der Waals crystals by raman spectroscopy: the case of black phosphorus.

The large foreseeable use two-dimensional materials in nanotechnology consequently demands precise methods for their thickness measurements. Usually, having a quick and easy methodology is a key requisite for the inspection of the large number of flakes produced by exfoliation methods. An effective option in this respect relies on the measurement of the intensity of Raman spectra, which can be used even when the flakes are encapsulated by a transparent protective layer. However, when using this methodology, special attention should be paid to the crystalline anisotropy of the examined material. Specifically, for the case of black phosphorus flakes, the absolute experimental determination of the thickness is rather difficult because the material is characterized by a low symmetry and also because the Raman tensors are complex quantities. In this work, we exploited Raman spectroscopy to measure the thickness of black phosphorous flakes using silicon as reference material for intensity calibrations. We found out that we can determine the thickness of a flake above 5 nm with an accuracy of about 20%. We tested the reproducibility of the method on two different setups, finding similar results. The method can be applied also to other van der Waals materials with a Raman band characterized by the same Raman tensor.

Nanoscale-Induced Formation of Silicide around Gold Nanoparticles Encapsulated in a-Si.

Decorating thin-film solar cells with plasmonic nanoparticles is being pursued in order to improve device efficiency through increased scattering and local field enhancement. Gold nanoparticles are particularly interesting due to their chemical inertness and plasmon resonance in the visible range of the spectrum. In this work, gold nanoparticles fabricated by a gas aggregation nanoparticle source and embedded in a-Si (a commercial solar cell material) are studied using X-ray photoelectron spectroscopy, transmission electron microscopy, electron energy-loss spectroscopy, and energy-dispersive X-ray spectroscopy. The formation of gold silicide around the nanoparticles is investigated, as it has important consequences for the optical and electronic properties of the structures. Different from previous studies, in which the silicide formation is observed for gold nanoparticles and thin films grown on top of crystalline silicon or silica, it is found that silicide formation is largely enhanced around the nanoparticles, owing to their increased surface/volume ratio. A detailed gold silicide formation mechanism is presented based on the results, and strategies for optimizing the design of plasmonically enhanced solar cells with gold nanoparticles encapsulated in a-Si are discussed.

Embedding epitaxial (blue) phosphorene in between device-compatible functional layers.

The newly predicted allotropic phase of phosphorus termed blue phosphorus has been recently synthesized in its two-dimensional (2D) single layer fashion via epitaxial growth on a Au(111) substrate. The large scale epitaxy and the semiconductive character with a reported bandgap of ∼1.1 eV suggest that epitaxial phosphorene might be a suitable candidate to overcome the lack of a sizeable bandgap in semimetal X-enes. In close similarity to other X-enes, like silicene, the epitaxial phosphorene shows technological issues towards possible integration into devices, such as the metallic supporting template at the bottom and oxidation under ambient conditions on the top interface of its 2D lattice. Here, we report on a detailed structural and chemical analysis of epitaxial phosphorene and a newly developed methodology to allow for easy transfer of the chemically protected epitaxial phosphorene in between amorphous Al2O3 and thin Au(111) films grown on mica. The large scale epitaxy achieved on a portable Au(111)/mica template and the low reactivity with molecular oxygen of phosphorene pave the way for easy encapsulation of epitaxial phosphorene fostering its exploitability in devices through a versatile transfer methodology, as in the case of epitaxial silicene.

Electroactive Ionic Soft Actuators with Monolithically Integrated Gold Nanocomposite Electrodes.

Electroactive ionic gel/metal nanocomposites are produced by implanting supersonically accelerated neutral gold nanoparticles into a novel chemically crosslinked ion conductive soft polymer. The ionic gel consists of chemically crosslinked poly(acrylic acid) and polyacrylonitrile networks, blended with halloysite nanoclays and imidazolium-based ionic liquid. The material exhibits mechanical properties similar to that of elastomers (Young's modulus ≈ 0.35 MPa) together with high ionic conductivity. The fabrication of thin (≈100 nm thick) nanostructured compliant electrodes by means of supersonic cluster beam implantation (SCBI) does not significantly alter the mechanical properties of the soft polymer and provides controlled electrical properties and large surface area for ions storage. SCBI is cost effective and suitable for the scaleup manufacturing of electroactive soft actuators. This study reports the high-strain electromechanical actuation performance of the novel ionic gel/metal nanocomposites in a low-voltage regime (from 0.1 to 5 V), with long-term stability up to 76 000 cycles with no electrode delamination or deterioration. The observed behavior is due to both the intrinsic features of the ionic gel (elasticity and ionic transport capability) and the electrical and morphological features of the electrodes, providing low specific resistance (<100 Ω cm-2 ), high electrochemical capacitance (≈mF g-1 ), and minimal mechanical stress at the polymer/metal composite interface upon deformation.