One-step chemically vapor deposited hybrid 1T-MoS2/2H-MoS2 heterostructures towards methylene blue photodegradation.

The photocatalytic degradation of methylene blue is a straightforward and cost-effective solution for water decontamination. Although many materials have been reported so far for this purpose, the proposed solutions inflicted high fabrication costs and low efficiencies. Here, we report on the synthesis of tetragonal (1T) and hexagonal (2H) mixed molybdenum disulfide (MoS2) heterostructures for an improved photocatalytic degradation efficiency by means of a single-step chemical vapor deposition (CVD) technique. We demonstrate that the 1T-MoS2/2H-MoS2 heterostructures exhibited a narrow bandgap âˆ¼ 1.7 eV, and a very low reflectance (<5%) under visible-light, owing to their particular vertical micro-flower-like structure. We exfoliated the CVD-synthesised 1T-MoS2/2H-MoS2 films to assess their photodegradation properties towards the standard methylene blue dye. Our results showed that the photo-degradation rate-constant of the 1T-MoS2/2H-MoS2 heterostructures is much greater under UV excitation (i.e., 12.5 × 10-3 min-1) than under visible light illumination (i.e., 9.2 × 10-3 min-1). Our findings suggested that the intermixing of the conductive 1T-MoS2 with the semi-conducting 2H-MoS2 phases favors the photogeneration of electron-hole pairs. More importantly, it promotes a higher efficient charge transfer, which accelerates the methylene blue photodegradation process.

Broadband photodetection using one-step CVD-fabricated MoS2/MoO2 microflower/microfiber heterostructures.

Molybdenum disulfide (MoS2) has been combined so far with other photodetecting semiconductors as an enhancing agent owing to its optical and electronic properties. Existing approaches demonstrated MoS2-incorporated photodetector devices using complex and costly fabrication processes. Here, we report on simplified one-step on the chemical vapor deposition (CVD) based synthesis of a unique microfiber/microflower MoS2-based heterostructure formed by capturing MoO2 intermediate material during the CVD process. This particular morphology engenders a material chemical and electronic interplay exalting the heterostructure absorption up to ~ 98% over a large spectral range between 200 and 1500 nm. An arsenal of characterization methods were used to elucidate the properties of these novel heterostructures including Raman spectroscopy, X-ray diffraction, X-ray photoelectron spectrometry, high-resolution transmission and scanning electron microscopies, and Kelvin probe force microscopy. Our findings revealed that the MoS2 and the MoO2 crystallize in the hexagonal and monoclinic lattices, respectively. The integration of the MoS2/MoO2 heterostructures into functional photodetectors revealed a strong photoresponse under both standard sun illumination AM1.5G and blue light excitation at 450 nm. Responsivity and detectivity values as high as 0.75 mA W-1 and 1.45 × 107 Jones, respectively, were obtained with the lowest light intensity of 20 mW cm-2 at only 1 V bias. These results demonstrate the high performances achieved by the unique MoS2/MoO2 heterostructure for broadband light harvesting and pave the way for their adoption in photodetection applications.

Optimizing the photochemical conversion of UV-vis light of silver-nanoparticles decorated TiO2 nanotubes based photoanodes.

Homogeneous decoration of TiO2 nanotubes (NTs) by Ag metallic nanoparticles (NPs) was carried out by a relatively simple photoreduction process. This Ag-NPs decoration was found to improve the photoconversion efficiency of the TiO2-NTs based photoanodes. The x-ray photoelectron spectroscopy and x-ray diffraction analyses confirmed that all the Ag-NPs are metallic and the underlying TiO2-NTs crystallize in the anatase phase after their annealing at 400 °C, respectively. Transmission electron microscopy observations have confirmed the effective decoration of the TiO2-NTs' surface by Ag-NPs, and allowed to measure the average Ag-NPs size, which was found to increase linearly from (4 ± 2) nm to (16 ± 4) nm when the photoreduction time is increased from 5 to 20 min. The diffuse reflectivity of the Ag-NPs decorated TiO2-NTs was found to decrease significantly as compared to the undecorated TiO2-NTs. Interestingly, the Ag-NPs decorated TiO2-NTs exhibited a significantly enhanced photochemical response, under visible radiation, with regards to the undecorated NTs. This enhancement was found to reach its maximum for the TiO2-NTs decorated with Ag-NPs having the optimal average diameter of ∼8.5 nm. The maximum photoconversion efficiency of Ag-NPs decorated TiO2-NTs was about two times greater than for the undecorated ones. This improved photo-electro-chemical response is believed to be associated with the additional absorption of visible light of Ag-NPs through the localized surface plasmon resonance phenomenon. This interpretation is supported by the fact that the photoluminescence intensity of the Ag-NPs decorated TiO2-NTs was found to decrease significantly as compared to undecorated NTs, due to charge carriers trapping in the Ag NPs. This demonstrates that Ag-NPs decoration promotes photogenerated charges separation in the TiO2-NTs, increasing thereby their capacity for current photogeneration. The surface decoration of TiO2 NTs by noble metals NPs is expected to impact positively the use of TiO2-NTs based photoanodes in some energetic applications such as hydrogen generation and photo-electrochemical solar cells.

Growth Mechanisms of Inductively-Coupled Plasma Torch Synthesized Silicon Nanowires and their associated photoluminescence properties.

Ultra-thin Silicon Nanowires (SiNWs) were produced by means of an industrial inductively-coupled plasma (ICP) based process. Two families of SiNWs have been identified, namely long SiNWs (up to 2-3 micron in length) and shorter ones (~100 nm). SiNWs were found to consist of a Si core (with diameter as thin as 2 nm) and a silica shell, of which the thickness varies from 5 to 20 nm. By combining advanced transmission electron microscopy (TEM) techniques, we demonstrate that the growth of the long SiNWs occurred via the Oxide Assisted Growth (OAG) mechanism, while the Vapor Liquid Solid (VLS) mechanism is responsible for the growth of shorter ones. Energy filtered TEM analyses revealed, in some cases, the existence of chapelet-like Si nanocrystals embedded in an otherwise silica nanowire. Such nanostructures are believed to result from the exposure of some OAG SiNWs to high temperatures prevailing inside the reactor. Finally, the intense photoluminescence (PL) of these ICP-grown SiNWs in the 620-950 nm spectral range is a clear indication of the occurrence of quantum confinement. Such a PL emission is in accordance with the TEM results which revealed that the size of nanostructures are indeed below the exciton Bohr radius of silicon.

Field electron emission enhancement of graphenated MWCNTs emitters following their decoration with Au nanoparticles by a pulsed laser ablation process.

A plasma-enhanced chemical vapor deposition (PECVD) process was adapted to alter the growth of multiwall carbon nanotubes (MWCNTs) so that graphene sheets grow out of their tips. Gold nanoparticle (Au-NP) decoration of graphenated MWCNTs (g-MWCNTs) was obtained by subsequent decoration by a pulsed laser deposition (PLD) process. By varying the number of laser ablation pulses (N(Lp)) in the PLD process, we were able to control the size of the gold nanoparticles and the surface coverage of the decorated g-MWCNTs. The presence of Au-NPs, preferentially located at the tip of the g-MWCNTs emitters, is shown to significantly improve the field electron emission (FEE) properties of the global g-MWCNT/Au-NP nanohybrid films. Indeed, the electric field needed to extract a current density of 0.1 µA cm(-)(2) from the g-MWCNT/Au-NP films was decreased from 2.68 V µm(-1) to a value as low as 0.96 V µm(-1). On the other hand, UV photoelectron spectroscopy (UPS) characterization revealed a decrease in the global work function of the Au-decorated g-MWCNT nanohybrids compared to that of bare g-MWCNT emitters. Surprisingly, the work function of g-MWCNT was found to decrease from 4.9 to 4.7 eV with the addition of Au-NPs-a value lower than the work function of both materials worth 5.2 and 4.9 eV for gold and g-MWCNT, respectively. Our results show that the N(Lp) dependence of the FEE characteristics of the g-MWCNT/Au-NP emitters correlates well with their work function changes. Fowler-Nordheim-theory-based calculations suggest that the significant FEE enhancement of the emitters is also caused by the Au-NPs acting as nanoscale electric field enhancers.

Photoelectrocatalytic degradation of carbamazepine using Ti/TiO2 nanostructured electrodes deposited by means of a pulsed laser deposition process.

The objective of the present work is to evaluate the potential of photoelectrocatalytic oxidation (PECO) process using Ti/TiO2 for the degradation of carbamazepine (CBZ). Ti/TiO2 prepared by pulsed laser deposition (PLD) has been used as a photo-catalyst in a photoelectrocatalytic cell. The PLD TiO2 coatings were found to be of anatase structure consisting of nanocrystallites of approximately 15nm in diameter. Factorial and central and extreme composite design methodologies were successively employed to define the optimal operating conditions for CBZ degradation. Several factors such as current intensity, treatment time, pollutant concentration and cathode material were investigated. Using a 2(4) factorial matrix, the best performance for CBZ degradation (53.5%) was obtained at a current intensity of 0.1 A during 120min of treatment time and when the vitreous carbon (VC) was used at the cathode in the presence of 10mgL(-1) of CBZ. Treatment time and pollutant concentration were found to be very meaningful for CBZ removal. The PECO process applied under optimal conditions (at current intensity of 0.3A during 120min in the presence of 10mgL(-1) of CBZ with VC at the cathode) is able to oxidize around 73.5% ±2.8% of CBZ and to ensure 21.2%±7.7% of mineralization. During PECO process, CBZ was mainly transformed to acridine and anthranilic acid. Microtox biotests (Vibrio fisheri) showed that the treated - effluent was not toxic. The pseudo-second order kinetic model (k2=6×10(-4)Lmg(-1)min(-1)) described very well the oxidation of CBZ.

Pulsed laser ablation based direct synthesis of single-wall carbon nanotube/PbS quantum dot nanohybrids exhibiting strong, spectrally wide and fast photoresponse.

Pulsed laser ablation for the direct synthesis of single-wall carbon nanotube/PbS-quantumdot(SWCNT/PbS-QD) nanohybrids is demonstrated. The latitude of the developed pulsed laser deposition process permits not only the control of the size of the PbS-QDs but also the straightforward integration of these novel SWCNT/PbS-QD nanohybrids into photoconductive (PC) devices. Thus, by optimizing the nanohybrid characteristics, PC devices exhibiting not only fast but also strong photoresponse (as high as 1350% at 405 nm) are achieved.

Enhanced UV photoresponse of KrF-laser-synthesized single-wall carbon nanotubes/n-silicon hybrid photovoltaic devices.

We report on the KrF-laser ablation synthesis, purification and photocurrent generation properties of single-wall carbon nanotubes (SWCNTs). The thermally purified SWCNTs are integrated into hybrid photovoltaic (PV) devices by spin-coating them onto n-Si substrates. These novel SWCNTs/n-Si hybrid devices are shown to generate significant photocurrent (PC) over the entire 250-1050 nm light spectrum with external quantum efficiencies (EQE) reaching up to ~23%. Our SWCNTs/n-Si hybrid devices are not only photoactive in the traditional spectral range of Si solar cells, but generate also significant PC in the UV domain (below 400 nm). This wider spectral response is believed to be the result of PC generation from both the SWCNTs themselves and the tremendous number of local p-n junctions created at the nanotubes/Si interface. To assess the prevalence of these two contributions, the EQE spectra and J-V characteristics of these hybrid devices were investigated in both planar and top-down configurations, as a function of SWCNTs' film thickness. A sizable increase in EQE in the near UV with respect to the silicon is observed in both configurations, with a more pronounced UV photoresponse in the planar mode, confirming thereby the role of SWCNTs in the photogeneration process. The PC generation is found to reach its maximum for an optimal the SWCNT film thickness, which is shown to correspond to the best trade-off between lowest electrical resistance and highest optical transparency. Finally, by analyzing the J-V characteristics of our SWCNTs/n-Si devices with an equivalent circuit model, we were able to point out the contribution of the various electrical components involved in the photogeneration process. The SWCNTs-based devices demonstrated here open up the prospect for their use in highly effective photovoltaics and/or UV-light sensors.

Electrical transport properties of single wall carbon nanotube/polyurethane composite based field effect transistors fabricated by UV-assisted direct-writing technology.

We report on the fabrication and transport properties of single-walled carbon nanotube (SWCNT)/polyurethane (PU) nanocomposite microfiber-based field effect transistors (FETs). UV-assisted direct-writing technology was used, and microfibers consisting of cylindrical micro-rods, having different diameters and various SWCNT loads, were fabricated directly onto SiO2/Si substrates in a FET scheme. The room temperature dc electrical conductivities of these microfibers were shown to increase with respect to the SWCNT concentrations in the nanocomposite, and were about ten orders of magnitude higher than that of the pure polyurethane, when the SWCNT load ranged from 0.1 to 2.5 wt% only. Our results show that for SWCNT loads ≤ 1.5 wt%, all the microfibers behave as a FET with p-type transport. The resulting FET exhibited excellent performance, with an I(on)/I(off) ratio of 105 and a maximum on-state current (I(on)) exceeding 70 µA. Correlations between the FET performance, SWCNTs concentration, and the microfiber diameters are also discussed.

The channel length effect on the electrical performance of suspended-single-wall-carbon-nanotube-based field effect transistors.

We report on the electrical performance of field effect transistor (FET) nanodevices based on suspended single-wall carbon nanotubes (SWCNTs) grown by our 'all-laser' synthesis process. The attractiveness of the proposed approach lies in the combination of standard microfabrication processing with the in situ 'all-laser' localized growth of SWCNTs, offering an affordable way of directly integrating SWCNTs into nanodevices. The 'all-laser' process uses the same KrF excimer laser (248 nm), first, to deposit the nanocatalyzed electrodes and, in a second step, to grow the SWCNTs in a suspended geometry, achieving thereby the lateral bridging of the electrodes. The nanocatalyzed electrodes consist of a multilayer stack sandwiching a catalyst nanolayer ( approximately 5 nm thick) composed of Co/Ni nanoparticles. The 'all-laser' grown SWCNTs ( approximately 1 nm diameter) are most often seen to self-assemble into bundles (10-20 nm diameter) and to bridge laterally the various gap lengths (in the 2-10 microm investigation range) separating adjacent electrodes. The suspended-SWCNT-based FETs were found to behave as p-type transistors, in air and at room temperature, with very high ON/OFF switching ratios (whose magnitude markedly increases as the active channel length is reduced). For the shortest gap (i.e. 2 microm), the suspended-SWCNT-based FETs exhibited not only an ON/OFF switching ratio in excess of seven orders of magnitude, but also an ON-state conductance as high as 3.26 microS. Their corresponding effective carrier mobility was estimated (at V(SD) = 100 mV) to a value of approximately 4000 cm(2) V(-1) s(-1), which is almost ten times higher than the hole mobility in single-crystal silicon at room temperature.

Enhanced photosusceptibility near Tc for the light-induced insulator-to-metal phase transition in vanadium dioxide.

We use optical-pump terahertz-probe spectroscopy to investigate the near-threshold behavior of the photoinduced insulator-to-metal (IM) transition in vanadium dioxide thin films. Upon approaching Tc a reduction in the fluence required to drive the IM transition is observed, consistent with a softening of the insulating state due to an increasing metallic volume fraction (below the percolation limit). This phase coexistence facilitates the growth of a homogeneous metallic conducting phase following superheating via photoexcitation. A simple dynamic model using Bruggeman effective medium theory describes the observed initial condition sensitivity.

Ultra-high oxidation resistance of suspended single-wall carbon nanotube bundles grown by an "all-laser" process.

Single-wall carbon nanotubes (SWCNTs) were laterally grown on SiO2/Si substrates by means of an "all-laser" growth process. Our "all-laser" process stands out by its exclusive use of the same pulsed UV laser, first, to deposit the CoNi nanocatalyst and, second, to grow SWCNTs through the laser ablation of a pure graphite target. The "all-laser" grown SWCNTs generally self-assemble into bundles (5-15 nm-diam.) sprouting from the CoNi nanocatalyst and laterally bridging the 2 microm gap separating adjacent catalysed electrodes (in either "suspended" or "on-substrate" geometries). A comparative study of the oxidation resistance of both suspended and on-substrate SWCNTs was achieved. The "all-laser" grown SWCNTs were subjected to annealing under flowing oxygen at temperatures ranging from 200 to 1100 degrees C. Systematic scanning electron microscopy observations combined with micro-Raman analyses revealed that more than 20% of suspended nanotubes were still stable at temperatures as high as 900 degrees C under flowing O2 while the on-substrate counterpart were completely burnt out at this temperature. Accordingly, the activation energy, as deduced from the Arrhenius plot, of the suspended SWCNTs is found to be as high as approximately 180 kJ mol(-1) (approximately 9 times higher than that of the on-substrate ones). The high quality (almost defect-free) of the nanotubes synthesized by the "all-laser" approach, their protected tips into the embedded CoNi catalyst nanolayer together with their suspended geometry are thought to be responsible for their unprecedented ultra-high oxidation resistance. This opens up new prospects for the use of these suspended nanotubes into nanodevices that have to operate under highly oxidizing environments.