Evolution of transition metal dichalcogenide films properties during chemical vapor deposition: from monolayer islands to nanowalls.

Unique properties possessed by transition metal dichalcogenides (TMD) attract much attention to investigation of their formation and dependence of their characteristics on the production process parameters. Here we investigate formation of TMD films during chemical vapor deposition (CVD) in the mixture of the thermally activated gaseous H2S and vaporized transition metals. Our observations of changes in morphology, Raman spectra, and photoluminescent (PL) properties in combination with in-situ measurements of electrical conductivity of the deposits formed at various precursors concentrations and CVD duration are evidencing on existence of particular stages in the TMD materials formation. Gradual transformation of PL spectra from trion to exciton type is detected for different stages of the material formation. Obtained results and proposed methods provide tailoring of TMD film characteristics demanded for the particular applications like photodetectors, photocatalyst, gas sensors.

Crystallization of Copper Films on Sapphire Substrate for Large-Area Single-Crystal Graphene Growth.

Chemical vapor deposition synthesis of graphene on polycrystalline copper substrates from methane is a promising technique for industrial production and application. However, the quality of grown graphene can be improved by using single-crystal copper (111). In this paper, we propose to synthesize graphene on epitaxial single-crystal Cu film deposited and recrystallized on a basal-plane sapphire substrate. The effect of film thickness, temperature, and time of annealing on the size of copper grains and their orientation is demonstrated. Under optimized conditions, the copper grains with the (111) orientation and a record size of several millimeters are obtained, and the single-crystal graphene is grown over their entire area. The high quality of synthesized graphene has been confirmed by Raman spectroscopy, scanning electron microscopy, and the sheet resistance measurements by the four point probe method.

Bioresource-derived colloidal nitrogen-doped graphene quantum dots as ultrasensitive and stable nanosensors for detection of cancer and neurotransmitter biomarkers.

Rapid and accurate detection of cancer and neurological diseases is a major issue that has received great attention recently to enable early therapy treatment. In this report, we utilize an atmospheric pressure microplasma system to convert a natural bioresource chitosan into nitrogen-doped graphene quantum dots (NGQDs) for photoluminescence (PL) based selective detection of cancer and neurotransmitter biomarkers. By adjusting the pH conditions during the detection, multiple biomolecules including uric acid (UA), folic acid (FA), epinephrine (EP), and dopamine (DA) can be simultaneously detected with high selectivity and sensitivity using a single material only. Linear relationships between the biomarker concentration and the PL intensity ratio are obtained starting from 0.8 to 100 µM with low limits of detection (LoDs) of 123.1, 157.9, 80.5, and 91.3 nM for UA, EP, FA, and DA, respectively. Our work provides an insight into the multiple biomarker detection using a single material only, which is beneficial for the early detection and diagnosis of cancer and neurological diseases, as well as the development of new drugs.

Field Electron Emission from Crumpled CVD Graphene Patterns Printed via Laser-Induced Forward Transfer.

A new approach to the fabrication of graphene field emitters on a variety of substrates at room temperature and in an ambient environment is demonstrated. The required shape and orientation of the graphene flakes along the field are created by the blister-based laser-induced forward transfer of CVD high-quality single-layer graphene. The proposed technique allows the formation of emitting crumpled graphene patterns without losing the quality of the initially synthesized graphene, as shown by Raman spectroscopy. The electron field emission properties of crumpled graphene imprints 1 × 1 mm2 in size were studied. The transferred graphene flakes demonstrated good adhesion and emission characteristics.

Magnetic nanoribbons with embedded cobalt grown inside single-walled carbon nanotubes.

Molecular magnetism and specifically magnetic molecules have recently gained plenty of attention as key elements for quantum technologies, information processing, and spintronics. Transition to the nanoscale and implementation of ordered structures with defined parameters is crucial for advanced applications. Single-walled carbon nanotubes (SWCNTs) provide natural one-dimensional confinement that can be implemented for encapsulation, nanosynthesis, and polymerization of molecules into nanoribbons. Recently, the formation of atomically precise graphene nanoribbons inside SWCNTs has been reported. However, there have been only a limited amount of approaches to form ordered magnetic structures inside the nanotube channels and the creation of magnetic nanoribbons is still lacking. In this work we synthesize and reveal the properties of cobalt-phthalocyanine based nanoribbons (CoPcNRs) encapsulated in SWCNTs. Raman spectroscopy, transmission electron microscopy, absorption spectroscopy, and density functional theory calculations allowed us to confirm the encapsulation and to reveal the specific fingerprints of CoPcNRs. The magnetic properties were studied by transverse magnetooptical Kerr effect measurements, which indicated a strong difference in comparison with the pristine unfilled SWCNTs due to the impact of Co incorporated atoms. We anticipate that this approach of polymerization of encapsulated magnetic molecules inside SWCNTs will result in a diverse class of protected low-dimensional ordered magnetic materials for various applications.

Single-step extraction of small-diameter single-walled carbon nanotubes in the presence of riboflavin.

We propose a novel approach to disperse and extract small-diameter single-walled carbon nanotubes (SWCNTs) using an aqueous solution of riboflavin and Sephacryl gel. The extraction of small-diameter semiconducting SWCNTs was observed, regardless of the initial diameter distribution of the SWCNTs. Dispersion of SWCNTs occurs due to the adsorption of π-conjugated isoalloxazine moieties on the surface of small-diameter nanotubes and interactions between hydroxy groups of ribityl chains with water. During the SWCNT extraction, specific adsorption of riboflavin to SWCNTs leads to the minimization of interactions between the SWCNTs and gel media. Our experimental findings are supported by ab initio calculations demonstrating the impact of the riboflavin wrapping pattern around the SWCNTs on their interaction with the allyl dextran gel.

Age-Specific Etiology of Severe Acute Respiratory Infections and Influenza Vaccine Effectivity in Prevention of Hospitalization in Russia, 2018-2019 Season.

The expansion and standardization of clinical trials, as well as the use of sensitive and specific molecular diagnostics methods, provide new information on the age-specific roles of influenza and other respiratory viruses in development of severe acute respiratory infections (SARI). Here, we present the results of the multicenter hospital-based study aimed to detect age-specific impact of influenza and other respiratory viruses (ORV). The 2018-2019 influenza season in Russia was characterized by co-circulation of influenza A(H1N1)pdm09 and A(H3N2) virus subtypes which were detected among hospitalized patients with SARI in 19.3% and 16.4%, respectively. RSV dominated among ORV (15.1% of total cases and 26.8% in infants aged ≤ 2 years). The most significant SARI agents in intensive care units were RSV and influenza A(H1N1)pdm09 virus, (37.3% and 25.4%, respectively, of PCR-positive cases). Hyperthermia was the most frequently registered symptom for influenza cases. In contrast, hypoxia, decreased blood O2 concentration, and dyspnea were registered more often in RSV, rhinovirus, and metapneumovirus infection in young children. Influenza vaccine effectiveness (IVE) against hospitalization of patients with PCR-confirmed influenza was evaluated using test-negative case-control design. IVE for children and adults was estimated to be 57.0% and 62.0%, respectively. Subtype specific IVE was higher against influenza A(H1N1)pdm09, compared to influenza A(H3N2) (60.3% and 45.8%, respectively). This correlates with delayed antigenic drift of the influenza A(H1N1)pdm09 virus and genetic heterogeneity of the influenza A(H3N2) population. These studies demonstrate the need to improve seasonal influenza prevention and control in all countries as states by the WHO Global Influenza Strategy for 2019-2030 initiative.

Preparation of Copper Surface for the Synthesis of Single-Layer Graphene.

Chemical vapor deposition synthesis of graphene on copper foil from methane is the most promising technology for industrial production. However, an important problem of the formation of the additional graphene layers during synthesis arises due to the strong roughness of the initial copper foil. In this paper, various approaches are demonstrated to form a smooth copper surface before graphene synthesis to reduce the amount of few layer graphene islands. Six methods of surface processing of copper foils are studied and the decrease of the roughness from 250 to as low as 80 nm is achieved. The correlation between foil roughness and the formation of the additional layer is demonstrated. Under optimized conditions of surface treatment, the content of the additional graphene layer drops from 9 to 2.1%. The quality and the number of layers of synthesized graphene are analyzed by Raman spectroscopy, scanning electron microscopy and measurements of charge mobility.

Helicity-Sensitive Plasmonic Terahertz Interferometer.

Plasmonic interferometry is a rapidly growing area of research with a huge potential for applications in the terahertz frequency range. In this Letter, we explore a plasmonic interferometer based on graphene field effect transistor connected to specially designed antennas. As a key result, we observe helicity- and phase-sensitive conversion of circularly polarized radiation into dc photovoltage caused by the plasmon-interference mechanism: two plasma waves, excited at the source and drain part of the transistor, interfere inside the channel. The helicity-sensitive phase shift between these waves is achieved by using an asymmetric antenna configuration. The dc signal changes sign with inversion of the helicity. A suggested plasmonic interferometer is capable of measuring the phase difference between two arbitrary phase-shifted optical signals. The observed effect opens a wide avenue for phase-sensitive probing of plasma wave excitations in two-dimensional materials.

Printing of Crumpled CVD Graphene via Blister-Based Laser-Induced Forward Transfer.

The patterning and transfer of a two-dimensional graphene film without damaging its original structure is an urgent and difficult task. For this purpose, we propose the use of the blister-based laser-induced forward transfer (BB-LIFT), which has proven itself in the transfer of such delicate materials. The ease of implementation of laser techniques reduces the number of intermediate manipulations with a graphene film, increasing its safety. The work demonstrates the promise of BB-LIFT of single-layer graphene from a metal surface to a SiO2/Si substrate. The effect of the parameters of this method on the structure of transferred graphene islands is investigated. The relevance of reducing the distance between irradiating and receiving substrates for the transfer of free-lying graphene is demonstrated. The reasons for the damage to the integrity of the carbon film observed in the experiments are discussed. The preservation of the original crystal structure of transferred graphene is confirmed by Raman spectroscopy.

Many-particle excitations in non-covalently doped single-walled carbon nanotubes.

Doping of single-walled carbon nanotubes leads to the formation of new energy levels which are able to participate in optical processes. Here, we investigate (6,5)-single walled carbon nanotubes doped in a solution of hydrochloric acid using optical absorption, photoluminescence, and pump-probe transient absorption techniques. We find that, beyond a certain level of doping, the optical spectra of such nanotubes exhibit the spectral features related to two doping-induced levels, which we assign to a localized exciton [Formula: see text] and a trion T, appearing in addition to an ordinary exciton [Formula: see text]. We evaluate the formation and relaxation kinetics of respective states and demonstrate that the kinetics difference between E1 and X energy levels perfectly matches the kinetics of the state T. This original finding evidences the formation of trions through nonradiative relaxation via the [Formula: see text] level, rather than via a direct optical excitation from the ground energy state of nanotubes.

Gyroscopic effect detection in the colliding-pulse hybridly mode-locked erbium-doped all-fiber ring soliton laser.

We report on the gyroscopic effect detection in the bidirectional ultra-short pulse hybridly mode-locked erbium-doped all-fiber ring soliton laser. Owing to the Kerr nonlinearity contribution through self-phase modulation and self-steepening effects to the carrier-to-envelope phase slip of both clockwise and counterclockwise solitons, wideband controllable tuning of a gyroscope bias point has been demonstrated by means of appropriate adjustment of either intracavity polarization or pump power. Angular velocity detected ranges from 0.12 deg/s to 90 deg/s while rotation sensitivity reaches 7 kHz/(deg/s) for 0.79 m2 single-coil ring gyroscope in agreement with a calculated scale factor value. The bias point drift responsible for the gyroscope resolution capabilities has been studied on long (during 35-h-long continuous operation experiment) and short (∼1 min) time scales.

Generation of stretched pulses and dissipative solitons at 2 µm from an all-fiber mode-locked laser using carbon nanotube saturable absorbers.

We demonstrate for the first time, to the best of our knowledge, a thulium-doped, all-fiber, mode-locked laser using a carbon nanotube saturable absorber, operating in the dissipative-soliton regime and the stretched-pulse-soliton regime. The net dispersion of the laser cavity is adjusted by inserting different lengths of normal dispersion fiber, resulting in different mode-locking regimes. These results could serve as a foundation for the optimization of mode-locked fiber-laser cavity design at the 2 µm wavelength region.

Generation regimes of bidirectional hybridly mode-locked ultrashort pulse erbium-doped all-fiber ring laser with a distributed polarizer.

We report on the stable picosecond and femtosecond pulse generation from the bidirectional erbium-doped all-fiber ring laser hybridly mode-locked with a coaction of a single-walled carbon nanotube-based saturable absorber and nonlinear polarization evolution that was introduced through the insertion of the short-segment polarizing fiber. Depending on the total intracavity dispersion value, the laser emits conservative solitons, transform-limited Gaussian pulses, or highly chirped stretched pulses with almost 20 nm wide parabolic spectrum in both clockwise (CW) and counterclockwise (CCW) directions of the ring. Owing to the polarizing action in the cavity, we have demonstrated for the first time, to the best of our knowledge, an efficient tuning of soliton pulse characteristics for both CW and CCW channels via an appropriate polarization control. We believe that the bidirectional laser presented may be highly promising for gyroscopic and other dual-channel applications.

Oxygen reduction by lithiated graphene and graphene-based materials.

Oxygen reduction reaction (ORR) plays a key role in lithium-air batteries (LABs) that attract great attention thanks to their high theoretical specific energy several times exceeding that of lithium-ion batteries. Because of their high surface area, high electric conductivity, and low specific weight, various carbons are often materials of choice for applications as the LAB cathode. Unfortunately, the possibility of practical application of such batteries is still under question as the sustainable operation of LABs with carbon cathodes is not demonstrated yet and the cyclability is quite poor, which is usually associated with oxygen reduced species side reactions. However, the mechanisms of carbon reactivity toward these species are still unclear. Here, we report a direct in situ X-ray photoelectron spectroscopy study of oxygen reduction by lithiated graphene and graphene-based materials. Although lithium peroxide (Li2O2) and lithium oxide (Li2O) reactions with carbon are thermodynamically favorable, neither of them was found to react even at elevated temperatures. As lithium superoxide is not stable at room temperature, potassium superoxide (KO2) prepared in situ was used instead to test the reactivity of graphene with superoxide species. In contrast to Li2O2 and Li2O, KO2 was demonstrated to be strongly reactive.

Probing structural inhomogeneity of graphene layers via nonlinear optical scattering.

Incoherent optical second harmonic generation (SHG) is studied from series of multilayer graphene samples of various thickness manufactured by chemical vapor deposition technique and deposited over 150 µm thick glass slides. Two different values of the correlation lengths are obtained from the linear and SHG indicatrices and reveal the existence of two types of optical scatterers. The first one is associated with homogeneous graphene areas, while the second one originates from wrinkles at the interdomain boundaries. Second harmonic imaging microscopy used to map the distribution of the second-order polarization at the nanoscale confirms the results of the nonlinear scattering data.

Optical properties of graphene nanoribbons encapsulated in single-walled carbon nanotubes.

We report the photoluminescence (PL) from graphene nanoribbons (GNRs) encapsulated in single-walled carbon nanotubes (SWCNTs). New PL spectral features originating from GNRs have been detected in the visible spectral range. PL peaks from GNRs have resonant character, and their positions depend on the ribbon geometrical structure in accordance with the theoretical predictions. GNRs were synthesized using confined polymerization and fusion of coronene molecules. GNR@SWCNTs material demonstrates a bright photoluminescence both in infrared (IR) and visible regions. The photoluminescence excitation mapping in the near-IR spectral range has revealed the geometry-dependent shifts of the SWCNT peaks (up to 11 meV in excitation and emission) after the process of polymerization of coronene molecules inside the nanotubes. This behavior has been attributed to the strain of SWCNTs induced by insertion of the coronene molecules.

Chiral-selective growth of single-walled carbon nanotubes on lattice-mismatched epitaxial cobalt nanoparticles.

Controlling chirality in growth of single-walled carbon nanotubes (SWNTs) is important for exploiting their practical applications. For long it has been conceptually conceived that the structural control of SWNTs is potentially achievable by fabricating nanoparticle catalysts with proper structures on crystalline substrates via epitaxial growth techniques. Here, we have accomplished epitaxial formation of monometallic Co nanoparticles with well-defined crystal structure, and its use as a catalyst in the selective growth of SWNTs. Dynamics of Co nanoparticles formation and SWNT growth inside an atomic-resolution environmental transmission electron microscope at a low CO pressure was recorded. We achieved highly preferential growth of semiconducting SWNTs (~90%) with an exceptionally large population of (6, 5) tubes (53%) in an ambient CO atmosphere. Particularly, we also demonstrated high enrichment in (7, 6) and (9, 4) at a low growth temperature. These findings open new perspectives both for structural control of SWNTs and for elucidating the growth mechanisms.

Broadband light-induced absorbance change in multilayer graphene.

We report the ultrafast light-induced absorbance change in CVD-grown multilayer graphene. Using femtosecond pump-probe measurements in 1100-1800 nm spectral range, we revealed broadband absorbance change when the probe photon energy was higher than that of the pump photon. The observed phenomenon is interpreted in terms of the Auger recombination and impact ionization playing a significant role in the dynamics of photoexcited carriers in graphene.

Selective growth of SWNTs on partially reduced monometallic cobalt catalyst.

SiO(2) supported cobalt (Co) catalyst could be partially reduced and anchored by unreduced Co ions during a carbon monoxide (CO) chemical vapor deposition (CVD) process. This resulted in the formation of sub-nanometre metallic Co clusters catalyzing the growth of single-walled carbon nanotubes (SWNTs) with a narrow diameter distribution.