In this work we explore the kinetics of single-crystal graphene growth as a function of nucleation density. In addition to the standard methods for suppressing nucleation of graphene by pretreatment ...of Cu foils using oxidation, annealing, and reduction of the Cu foils prior to growth, we introduce a new method that further reduces the graphene nucleation density by interacting directly with the growth process at the onset of nucleation. The successive application of these two methods results in roughly 3 orders of magnitude reduction in graphene nucleation density. We use a kinetic model to show that at vanishingly low nucleation densities carbon incorporation occurs by a cooperative island growth mechanism that favors the formation of substrate-size single-crystal graphene. The model reveals that the cooperative growth of millimeter-size single-crystal graphene grains occurs by roughly 3 orders of magnitude increase in the reactive sticking probability of methane compared to that in random island nucleation.
Carbon nanotube (CNT) based microelectrodes exhibit rapid and selective detection of neurotransmitters. While different fabrication strategies and geometries of CNT microelectrodes have been ...characterized, relatively little research has investigated ways to selectively enhance their electrochemical properties. In this work, we introduce two simple, reproducible, low-cost, and efficient surface modification methods for carbon nanotube yarn microelectrodes (CNTYMEs): O2 plasma etching and antistatic gun treatment. O2 plasma etching was performed by a microwave plasma system with oxygen gas flow and the optimized time for treatment was 1 min. The antistatic gun treatment flows ions by the electrode surface; two triggers of the antistatic gun was the optimized number on the CNTYME surface. Current for dopamine at CNTYMEs increased 3-fold after O2 plasma etching and 4-fold after antistatic gun treatment. When the two treatments were combined, the current increased 12-fold, showing the two effects are due to independent mechanisms that tune the surface properties. O2 plasma etching increased the sensitivity due to increased surface oxygen content but did not affect surface roughness while the antistatic gun treatment increased surface roughness but not oxygen content. The effect of tissue fouling on CNT yarns was studied for the first time, and the relatively hydrophilic surface after O2 plasma etching provided better resistance to fouling than unmodified or antistatic gun treated CNTYMEs. Overall, O2 plasma etching and antistatic gun treatment improve the sensitivity of CNTYMEs by different mechanisms, providing the possibility to tune the CNTYME surface and enhance sensitivity.
Understanding the relative humidity (RH) response of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) is critical for improving the stability of organic electronic devices and ...developing selective sensors. In this work, combined gravimetric sensing, nanoscale surface probing, and mesoscale optoelectronic characterization are used to directly compare the RH dependence of electrical and optical conductivities and unfold connections between the rate of water adsorption and changes in functional properties of PEDOT:PSS film. We report three distinct regimes where changes in electrical conductivity, optical conductivity, and optical bandgap are correlated with the mass of adsorbed water. At low (RH < 25%) and high (RH > 60%) humidity levels, dramatic changes in electrical, optical, and structural properties occur, while changes are insignificant in mid-RH (25 < RH < 60%) conditions. We associate the three regimes with water adsorption at hydrophilic moieties at low RH, diffusion and swelling throughout the film at mid-RH, and saturation of the film by water at high RH. Optical film thickness increased by 150% as RH was increased from 9 to 80%. Low frequency (1 kHz) impedance increased by ∼100%, and film capacitance increased by ∼30% as RH increased from 9 to 80% due to an increase in the film dielectric constant. Changes in electrical and optical conductivities concomitantly decrease across the full range of RH tested.
Carbon nanotube (CNT) based microelectrodes exhibit rapid and selective detection of neurotransmitters. While different fabrication strategies and geometries of CNT microelectrodes have been ...characterized, relatively little research has investigated ways to selectively enhance their electrochemical properties. In this work, we introduce two simple, reproducible, low-cost, and efficient surface modification methods for carbon nanotube yarn microelectrodes (CNTYMEs): O
plasma etching and antistatic gun treatment. O
plasma etching was performed by a microwave plasma system with oxygen gas flow and the optimized time for treatment was 1 min. The antistatic gun treatment flows ions by the electrode surface; two triggers of the antistatic gun was the optimized number on the CNTYME surface. Current for dopamine at CNTYMEs increased 3-fold after O
plasma etching and 4-fold after antistatic gun treatment. When the two treatments were combined, the current increased 12-fold, showing the two effects are due to independent mechanisms that tune the surface properties. O
plasma etching increased the sensitivity due to increased surface oxygen content but did not affect surface roughness while the antistatic gun treatment increased surface roughness but not oxygen content. The effect of tissue fouling on CNT yarns was studied for the first time, and the relatively hydrophilic surface after O
plasma etching provided better resistance to fouling than unmodified or antistatic gun treated CNTYMEs. Overall, O
plasma etching and antistatic gun treatment improve the sensitivity of CNTYMEs by different mechanisms, providing the possibility to tune the CNTYME surface and enhance sensitivity.
A new approach to generate a two‐photon up‐conversion photoluminescence (PL) by directly exciting the gap states with continuous‐wave (CW) infrared photoexcitation in solution‐processing quasi‐2D ...perovskite films (PEA)2(MA)4Pb5Br16 with n = 5 is reported. Specifically, a visible PL peaked at 520 nm is observed with the quadratic power dependence by exciting the gap states with CW 980 nm laser excitation, indicating a two‐photon up‐conversion PL occurring in quasi‐2D perovskite films. Decreasing the gap states by reducing the n value leads to a dramatic decrease in the two‐photon up‐conversion PL signal. This confirms that the gap states are indeed responsible for generating the two‐photon up‐conversion PL in quasi‐2D perovskites. Furthermore, mechanical scratching indicates that the different‐n‐value nanoplates are essentially uniformly formed in the quasi‐2D perovskite films toward generating multi‐photon up‐conversion light emission. More importantly, the two‐photon up‐conversion PL is found to be sensitive to an external magnetic field, indicating that the gap states are essentially formed as spatially extended states ready for multi‐photon excitation. Polarization‐dependent up‐conversion PL studies reveal that the gap states experience the orbit–orbit interaction through Coulomb polarization to form spatially extended states toward developing multi‐photon up‐conversion light emission in quasi‐2D perovskites.
Gap states present a new approach to develop multi‐photon upconversion light emission in quasi‐2D perovskite films under continuous‐wave infrared excitation. Magneto‐photoluminescence (PL) and polarization‐dependent PL reveal that the gap states are essentially spatially extended states involved in orbit–orbit interaction toward generating multi‐photon excitation in quasi‐2D perovskite films.
The attractive optoelectronic properties of conducting polymers depend sensitively upon intra- and inter-polymer chain interactions, and therefore new methods to manipulate these interactions are ...continually being pursued. Here, we report a study of the isotopic effects of deuterium substitution on the structure, morphology and optoelectronic properties of regioregular poly(3-hexylthiophene)s with an approach that combines the synthesis of deuterated materials, optoelectronic properties measurements, theoretical simulation and neutron scattering. Selective substitutions of deuterium on the backbone or side-chains of poly(3-hexylthiophene)s result in distinct optoelectronic responses in poly(3-hexylthiophene)/6,6-phenyl-C61-butyric acid methyl ester (PCBM) photovoltaics. Specifically, the weak non-covalent intermolecular interactions induced by the main-chain deuteration are shown to change the film crystallinity and morphology of the active layer, consequently reducing the short-circuit current. However, side-chain deuteration does not significantly modify the film morphology but causes a decreased electronic coupling, the formation of a charge transfer state, and increased electron-phonon coupling, leading to a remarkable reduction in the open circuit voltage.
We demonstrate that UV-light activation of polycrystalline ZnO films on flexible polyimide (Kapton) substrates can be used to detect and differentiate between environmental changes in oxygen and ...water vapor. The in-plane resistive and impedance properties of ZnO films, fabricated from bacteria-derived ZnS nanoparticles, exhibit unique resistive and capacitive responses to changes in O2 and H2O. We propose that the distinctive responses to O2 and H2O adsorption on ZnO could be utilized to statistically discriminate between the two analytes. Molecular dynamic simulations (MD) of O2 and H2O adsorption energy on ZnO surfaces were performed using the large-scale Atomic/Molecular Massively Parallel Simulator (LAMMPS) with a reactive force-field (ReaxFF). These simulations suggest that the adsorption mechanisms differ for O2 and H2O adsorption on ZnO, and are governed by the surface termination and the extent of surface hydroxylation. Electrical response measurements, using DC resistance, AC impedance spectroscopy, and Kelvin Probe Force Microscopy (KPFM), demonstrate differences in response to O2 and H2O, confirming that different adsorption mechanisms are involved. Statistical and machine learning approaches were applied to demonstrate that by integrating the electrical and kinetic responses the flexible ZnO sensor can be used for detection and discrimination between O2 and H2O at low temperature.
The structure of vanadium oxide species supported on ceria (VO x /CeO2) was investigated under various conditions by in situ multiwavelength Raman spectroscopy, IR spectroscopy, isotopic labeling, ...and temperature-programmed reduction (TPR). For the first time, the detailed structure of dehydrated VO x species was revealed on the polycrystalline ceria support. VO x species can coexist on ceria surface in the structure of monomer, dimer, trimer, polymer, crystalline V2O5, and CeVO4 as a function of VO x loading. These species interact strongly with both the defect sites and labile surface oxygen of ceria, passivating the redox property of ceria. Under ambient condition, the dispersed VO x species are hydrated into polyvanadate species that can be reversibly dehydrated back to the original structure forms. The ceria support with defect sites facilitates the interaction between water (H2 18O) and V16O x species, leading to very facile isotopic oxygen exchange between the two even at room temperature. During H2 reduction, both the VO x species and the ceria support can be reduced with ceria surface being more reducible. The reducibility of various dispersed VO x species scales with their polymerization degree, that is, polymer > trimer > dimer > monomer. The reoxidation of reduced VO x species is found to proceed via ceria lattice oxygen instead of the gas phase oxygen where ceria acts as an oxygen buffer. The revealed structure evolution of surface VO x species on ceria under hydrated, dehydrated, reduced, and regenerated conditions provides a basis for understanding the vanadia-ceria catalysis.
Chymotrypsin is an important proteolytic enzyme in the human digestive system that cleaves milk proteins through the hydrolysis reaction, making it an interesting subject to study the activity of ...milk proteases. In this work, we compared detection of chymotrypsin by spectrophotometric dynamic light scattering (DLS) and quartz crystal microbalance (QCM) methods and determined the limit of chymotrypsin detection (LOD), 0.15 ± 0.01 nM for spectrophotometric, 0.67 ± 0.05 nM for DLS and 1.40 ± 0.30 nM for QCM methods, respectively. The sensors are relatively cheap and are able to detect chymotrypsin in 3035 min. While the optical detection methods are simple to implement, the QCM method is more robust for sample preparation, and allows detection of chymotrypsin in non-transparent samples. We give an overview on methods and instruments for detection of chymotrypsin and other milk proteases.
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