Tuning the electronic properties of monolayer and bilayer transition metal dichalcogenide compounds under direct out-of-plane compression

The band-gap modulation of atomically thin semiconductor transition metal dichalcogenides (MX; M = Mo or W, X = S or Se) under direct out-of-plane compression is systematically studied by means of the density functional theory (DFT) formalism including spin-orbit coupling (SOC) and dispersion correction (D3). The out-of-plane compared with other regimes stress regime significantly reduces the pressure threshold at which the semimetal state is achieved (2.7-3.1 and 1.9-3.2 GPa for mono- and bilayer systems, respectively). Structural, electronic and bonding properties are investigated for a better understanding of the electronic transitions achieved with compression. A notable relationship with the formal ionic radius (M and X) is obtained. On one hand, the monolayer systems with the smallest transition metal radius (Mo < W) reach the semimetal state at lower stress, on the other hand, for bilayer specimens the transition to semimetal is observed earlier for compounds with the smallest chalcogenide radius (S < Se). Moreover, the appearance of non-covalent interaction (NCI) domains in the semimetal state confirms that the out-of-plane compression promotes the interaction between sulfur atoms in the single layered systems and reduces the interlayer space in bilayer configurations. Our predictions, supported by experimental evidences in the case of monolayered MoS, demonstrate new alternative methods for tuning the electronic properties of transition metal dichalcogenides under direct out-of-plane compression

Thermally Tunable Dual Emission of the d^8–d^8 Dimer [Pt_2(μ-P_2O_5(BF_2)_2)_4]^(4–)

High-resolution fluorescence, phosphorescence, as well as related excitation spectra, and, in particular, the emission decay behavior of solid [Bu_4N]_4[Pt_2(μ-P_2O_5(BF_2)_2)_4], abbreviated Pt(pop-BF_2), have been investigated over a wide temperature range, 1.3–310 K. We focus on the lowest excited states that result from dσ^*pσ (5d_z2–6p_z) excitations, i.e., the singlet state S_1 (of ^1A_2u symmetry in D_(4h)) and the lowest triplet T_1, which splits into spin–orbit substates A_(1u)(^3A_(2u)) and E_u(^3A_(2u)). After optical excitation, an unusually slow intersystem crossing (ISC) is observed. As a consequence, the compound shows efficient dual emission, consisting of blue fluorescence and green phosphorescence with an overall emission quantum yield of ∼100% over the investigated temperature range. Our investigation sheds light on this extraordinary dual emission behavior, which is unique for a heavy-atom transition metal compound. Direct ISC processes in Pt(pop-BF_2) are largely forbidden due to spin-, symmetry-, and Franck–Condon overlap-restrictions and, therefore, the ISC time is as long as 29 ns for T < 100 K. With temperature increase, two different thermally activated pathways, albeit still relatively slow, are promoted by spin-vibronic and vibronic mechanisms, respectively. Thus, distinct temperature dependence of the ISC processes results and, as a consequence, also of the fluorescence/phosphorescence intensity ratio. The phosphorescence lifetime also is temperature-dependent, reflecting the relative population of the triplet T_1 substates E_u and A_(1u). The highly resolved phosphorescence shows a ∼220 cm^(–1) red shift below 10 K, attributable to zero-field splitting of 40 cm^(–1) plus a promoting vibration of 180 cm^(–1)

Optical Near-Field Electron Microscopy

Imaging dynamical processes at interfaces and on the nanoscale is of great importance throughout science and technology. While light-optical imaging techniques often cannot provide the necessary spatial resolution, electron-optical techniques damage the specimen and cause dose-induced artefacts. Here, Optical Near-field Electron Microscopy (ONEM) is proposed, an imaging technique that combines non-invasive probing with light, with a high spatial resolution read-out via electron optics. Close to the specimen, the optical near-fields are converted into a spatially varying electron flux using a planar photocathode. The electron flux is imaged using low energy electron microscopy, enabling label-free nanometric resolution without the need to scan a probe across the sample. The specimen is never exposed to damaging electrons

On the Suitability of Raman Spectroscopy to Monitor the Degree of Graphene Functionalization by Diazonium Salts

Raman spectroscopy is undoubtedly the most frequently used technique for universal characterization of graphene and related materials. Quantification of parameters like disorder or strain is possible through analysis of particular Raman bands. However, under certain conditions, such evaluation can be jeopardized by - sometimes hidden - convolution of more overlapping effects. In this work, graphene functionalization by the common nitrobenzenediazonium salt under simultaneous biaxial tensile deformation induced by substrate swelling was investigated by Raman spectroscopy. As expected, the disorder-related D band appeared in the spectra documenting the covalent attack on the graphene lattice. However, the strain-induced shift of the graphene bands exposed additional peaks, masked at exactly the same positions as the unstrained graphene bands. The new bands were assigned to vibrations of the diazonium molecule and its decomposition products adsorbed on top of the functionalized graphene. The external strain thus provided means for more correct quantification of the lattice disorder

Electrical Contact Resistance of Large-Area Graphene on Pre-Patterned Cu and Au Electrodes

Contact resistance between electrically connected parts of electronic elements can negatively affect their resulting properties and parameters. The contact resistance is influenced by the physicochemical properties of the connected elements and, in most cases, the lowest possible value is required. The issue of contact resistance is also addressed in connection with the increasingly frequently used carbon allotropes. This work aimed to determine the factors that influence contact resistance between graphene prepared by chemical vapour deposition and pre-patterned Cu and Au electrodes onto which graphene is subsequently transferred. It was found that electrode surface treatment methods affect the resistance between Cu and graphene, where contact resistance varied greatly, with an average of 1.25 ± 1.54 kΩ, whereas for the Au electrodes, the deposition techniques did not influence the resulting contact resistance, which decreased by almost two orders of magnitude compared with the Cu electrodes, to 0.03 ± 0.01 kΩ

Effect of steam-treatment time on the length and structure of single-walled and double-walled carbon nanotubes

A major challenge to turn the potential of carbon nanotubes (CNTs) into customer applications is to reduce or eliminate their toxicity. Taking into account health and safety concerns, intensified research efforts have been conducted to improve the biocompatibility of CNTs, including the development of new shortening and purification strategies. Ideally, the methods used for improving the biocompatibility of CNTs should not alter the electronic properties of CNTs. Herein, we report on the shortening of a sample containing single-walled and double-walled CNTs using steam and obtain new insights in the properties of the steam-treated CNTs. The present study shows that short CNTs (median length ca. 200 nm) can be obtained under the reported conditions. Raman analysis reveals that wider and outer nanotubes undergo more significant changes than the narrower and inner ones, especially after a prolonged steam treatment

A tool box to ascertain the nature of doping and photoresponse in single-walled carbon nanotubes

The effect of doping on the electronic properties in bulk single-walled carbon nanotube (SWCNT) samples is studied for the first time using a new in situ Raman spectroelectrochemical method, and further verified by DFT calculations and photoresponse. We use p-/n-doped SWCNTs prepared by diazonium reactions as a versatile chemical strategy to control the SWCNT behavior. The measured and calculated data testify an acceptor effect of 4-aminobenzenesulfonic acid (p-doping), and a donor effect (n-doping) in the case of benzyl alcohol. In addition, pristine and covalently functionalized SWCNTs were used for the preparation of photoactive film electrodes. The photocathodic current in the photoelectrochemical cell is consistently modulated by the doping group. These results validate the in situ Raman spectroelectrochemistry as a unique tool box for predicting the electronic properties of functionalized SWCNTs in the form of thin films and their operational functionality in thin film devices for future optoelectronic applications

Electrical Contact Resistance of Large-Area Graphene on Pre-Patterned Cu and Au Electrodes

Contact resistance between electrically connected parts of electronic elements can negatively affect their resulting properties and parameters. The contact resistance is influenced by the physicochemical properties of the connected elements and, in most cases, the lowest possible value is required. The issue of contact resistance is also addressed in connection with the increasingly frequently used carbon allotropes. This work aimed to determine the factors that influence contact resistance between graphene prepared by chemical vapour deposition and pre-patterned Cu and Au electrodes onto which graphene is subsequently transferred. It was found that electrode surface treatment methods affect the resistance between Cu and graphene, where contact resistance varied greatly, with an average of 1.25 ± 1.54 kΩ, whereas for the Au electrodes, the deposition techniques did not influence the resulting contact resistance, which decreased by almost two orders of magnitude compared with the Cu electrodes, to 0.03 ± 0.01 kΩ.Contact resistance between electrically connected parts of electronic elements can negatively affect their resulting properties and parameters. The contact resistance is influenced by the physicochemical properties of the connected elements and, in most cases, the lowest possible value is required. The issue of contact resistance is also addressed in connection with the increasingly frequently used carbon allotropes. This work aimed to determine the factors that influence contact resistance between graphene prepared by chemical vapour deposition and pre-patterned Cu and Au electrodes onto which graphene is subsequently transferred. It was found that electrode surface treatment methods affect the resistance between Cu and graphene, where contact resistance varied greatly, with an average of 1.25 ± 1.54 kΩ, whereas for the Au electrodes, the deposition techniques did not influence the resulting contact resistance, which decreased by almost two orders of magnitude compared with the Cu electrodes, to 0.03 ± 0.01 kΩ

Identificación de plagas de chapulín en el norte–centro de México

Short carbon nanotubes (CNTs) are desired for a variety of applications. As a consequence, several strategies have been reported to cut and shorten the length of as-produced CNTs via chemical and physical routes. The efficiency of a given strategy largely depends on the physico-chemical characteristics of the CNTs employed. In order to be able to directly compare the advantages and disadvantages of commonly used protocols, a single batch of chemical vapor deposition single-walled CNTs (SWCNTs) and a batch of multi-walled CNTs (MWCNTs) were subjected to four cutting/shortening strategies, namely acid cutting, piranha treatment, steam shortening and ball milling. The length distribution was assessed by means of scanning electron microscopy. Sample purity and CNT wall structure were determined by Raman spectroscopy, thermogravimetric analysis and magnetic measurements. Within the employed experimental conditions, piranha treatment turned out to be the most efficient to achieve short SWCNTs with a narrow length distribution in a good yield, whereas a mixture of sulfuric/nitric acid was preferred in the case of MWCNTs. A subsequent short steam treatment allowed to remove functional groups present in the samples, leading to median length distributions of 266 nm and 225 nm for SWCNTs and MWCNTs respectively after the combined protocols