Molybdenum Carbamate Nanosheets as a New Class of Potential Phase Change Materials.

We report for the first time the synthesis of large, free-standing, Mo2O2(µ-S)2(Et2dtc)2 (MoDTC) nanosheets (NSs), which exhibit an electron-beam induced crystalline-to-amorphous phase transition. Both electron beam ionization and femtosecond (fs) optical excitation induce the phase transition, which is size-, morphology-, and composition-preserving. Resulting NSs are the largest, free-standing regularly shaped two-dimensional amorphous nanostructures made to date. More importantly, amorphization is accompanied by dramatic changes to the NS electrical and optical response wherein resulting amorphous species exhibit room-temperature conductivities 5 orders of magnitude larger than those of their crystalline counterparts. This enhancement likely stems from the amorphization-induced formation of sulfur vacancy-related defects and is supported by temperature-dependent transport measurements, which reveal efficient variable range hopping. MoDTC NSs represent one instance of a broader class of transition metal carbamates likely having applications because of their intriguing electrical properties as well as demonstrated ability to toggle metal oxidation states.

Wash-Durable Conductive Yarn with Ethylene Glycol-Treated PEDOT:PSS for Wearable Electric Heaters.

Recently, wearable electric heaters with high durability and low-power operation have attracted much attention due to their potential to change traditional approaches for personal heating management and thermal therapy systems. Here, we report textile-based wearable heaters based on highly durable conductive yarns, which were transformed from traditional cotton yarns through a facile dyeing process of poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) and ethylene glycol (EG). With the EG post-treatment, the conductive yarns exhibited an electrical conductivity of ∼76 S cm-1 and good stability under repeated cycles of washing and drying. The heating elements made from the conductive yarns showed an excellent distribution of temperature and could be heated up to 150 °C at a sufficiently low driving voltage of 5 V. Also, the heating elements showed stable Joule heating performance under repeated bending stress and 2000 cycles of stretching and releasing. To demonstrate its practical use for on-body heating systems, a lightweight and air-breathable thermal wristband was demonstrated by sewing the conductive yarns onto a fabric with a simple circuit structure. From these results, we believe that our strategy to obtain highly conductive and durable yarns can be utilized in various applications, including medical heat therapy and personal heating management systems.

Highly sensitive polyaniline-coated fiber gas sensors for real-time monitoring of ammonia gas.

A single-yarn-based gas sensor has been made from conductive polyaniline coated on commercial yarns. This can detect ammonia gas concentration in an environment or a working area. Cotton, rayon and polyester are utilized as substrates using a dip-coating process. The conductive yarns show ohmic behavior with an electrical resistance of 15-31 kΩ cm-1. The conductive polyester yarn exhibits higher mechanical strength even after intensive chemical treatment. It also has the highest gas response of 57% of 50 ppm ammonia gas, the concentration at which health problems will occur. A linear gas response of the yarn sensor appears in a range of 5-25 ppm ammonia concentration. The polyester yarn sensor can be reused without any change in its sensing response. It can monitor gas levels continuously giving real-time results. By using a microcontroller as part of the circuitry, the gas detection results are transferred and updated wirelessly to a computer or to a smartphone. The textile-based gas sensor can be sewn directly onto the fabrics since it is made with the same fabric. This single-yarn-based gas sensor is suitable for mass production and is appropriate for sophisticated applications.

Light induced nanowire assembly: the electrostatic alignment of semiconductor nanowires into functional macroscopic yarns.

The electrostatic alignment and directed assembly of semiconductor nanowires into macroscopic, centimeter-long yarns is demonstrated. Different morphologies can be produced, including longitudinally segmented/graded yarns or mixed composition fibers. Nanowire yarns display long range photoconductivities and open up exciting opportunities for potential use in future nanowire-based textiles or in solar photovoltaics.

Controlled synthesis of compositionally tunable ternary PbSe(x)S(1-x) as well as binary PbSe and PbS nanowires.

High-quality compositionally tunable ternary PbSe(x)S(1-x) (x = 0.23, 0.39, 0.49, 0.68, and 0.90) nanowires (NWs) and their binary analogues have been grown using solution-liquid-solid growth with lead(II) diethyldithiocarbamate, Pb(S(2)CNEt(2))(2), and lead(II) imido(bis(selenodiisopropylphosphinate)), Pb((SeP(i)Pr(2))(2)N)(2), as single-source precursors. The alloyed nature of PbSe(x)S(1-x) wires was confirmed using ensemble X-ray diffraction and energy dispersive X-ray spectroscopy (EDXS). Single NW EDXS line scans taken along the length of individual wires show no compositional gradients. NW compositions were independently confirmed using inductively coupled plasma atomic emission spectroscopy. Slight stoichiometric deviations occur but never exceed 13.3% of the expected composition, based on the amount of introduced precursor. In all cases, resulting nanowires have been characterized using transmission electron microscopy. Mean diameters are between 9 and 15 nm with accompanying lengths that range from 4 to 10 µm. Associated selected area electron diffraction patterns indicate that the PbSe(x)S(1-x), PbSe, and PbS NWs all possess the same <002> growth direction, with diffraction patterns consistent with an underlying rock salt crystal structure.

Synthetic Strategy and Structural and Optical Characterization of Thin Highly Crystalline Titanium Disulfide Nanosheets.

Two-dimensional (2D) nanomaterials have recently received significant attention because of their attractiveness for use in many nanostructured devices. Layered transition-metal dichalcogenides are of particular interest because reducing their dimensionality causes changes in their already anisotropic physical and chemical properties. The present study describes the first bottom-up solution-phase synthesis of thin highly crystalline titanium disulfide (TiS2) nanosheets (NSs) using abundant low-cost molecular precursors. The obtained TiS2 NSs have average dimensions of ∼500 nm × 500 nm in the basal plane and have thicknesses of ∼5 nm. They exhibit broad absorption in the visible that tails out into the near-infrared. The obtained results demonstrate new opportunities in synthesizing low-dimensional 2D nanomaterials with potential use in various photochemical energy applications.

Photocatalytic Hydrogen Generation Efficiencies in One-Dimensional CdSe Heterostructures.

To better understand the role nanoscale heterojunctions play in the photocatalytic generation of hydrogen, we have designed several model one-dimensional (1D) heterostructures based on CdSe nanowires (NWs). Specifically, CdSe/CdS core/shell NWs and Au nanoparticle (NP)-decorated core and core/shell NWs have been produced using facile solution chemistries. These systems enable us to explore sources for efficient charge separation and enhanced carrier lifetimes important to photocatalytic processes. We find that visible light H2 generation efficiencies in the produced hybrid 1D structures increase in the order CdSe < CdSe/Au NP < CdSe/CdS/Au NP < CdSe/CdS with a maximum H2 generation rate of 58.06 ± 3.59 µmol h(-1) g(-1) for CdSe/CdS core/shell NWs. This is 30 times larger than the activity of bare CdSe NWs. Using femtosecond transient differential absorption spectroscopy, we subsequently provide mechanistic insight into the role nanoscale heterojunctions play by directly monitoring charge flow and accumulation in these hybrid systems. In turn, we explain the observed trend in H2 generation rates with an important outcome being direct evidence for heterojunction-influenced charge transfer enhancements of relevant chemical reduction processes.

Charge carrier trapping and acoustic phonon modes in single CdTe nanowires.

Semiconductor nanostructures produced by wet chemical synthesis are extremely heterogeneous, which makes single particle techniques a useful way to interrogate their properties. In this paper the ultrafast dynamics of single CdTe nanowires are studied by transient absorption microscopy. The wires have lengths of several micrometers and lateral dimensions on the order of 30 nm. The transient absorption traces show very fast decays, which are assigned to charge carrier trapping into surface defects. The time constants vary for different wires due to differences in the energetics and/or density of surface trap sites. Measurements performed at the band edge compared to the near-IR give slightly different time constants, implying that the dynamics for electron and hole trapping are different. The rate of charge carrier trapping was observed to slow down at high carrier densities, which was attributed to trap-state filling. Modulations due to the fundamental and first overtone of the acoustic breathing mode were also observed in the transient absorption traces. The quality factors for these modes were similar to those measured for metal nanostructures, and indicate a complex interaction with the environment.

Low temperature solution-phase growth of ZnSe and ZnSe/CdSe core/shell nanowires.

High quality ZnSe nanowires (NWs) and complementary ZnSe/CdSe core/shell species have been synthesized using a recently developed solution-liquid-solid (SLS) growth technique. In particular, bismuth salts as opposed to pre-synthesized Bi or Au/Bi nanoparticles have been used to grow NWs at low temperatures in solution. Resulting wires are characterized using transmission electron microscopy and possess mean ensemble diameters between 15 and 28 nm with accompanying lengths ranging from 4-10 µm. Subsequent solution-based overcoating chemistry results in ZnSe wires covered with CdSe nanocrystals. By varying the shell's growth time, different thicknesses can be obtained and range from 8 to 21 nm. More interestingly, the mean constituent CdSe nanocrystal diameter can be varied and results in size-dependent shell emission spectra.