Xiaoxian Zhang

Superfast-Response and Ultrahigh-Power-Density Electromechanical Actuators Based on Hierarchal Carbon Nanotube Electrodes and Chitosan

Here we report a novel single-walled carbon nanotube (SWNT) based bimorph electromechanical actuator, which consists of unique as-grown SWNT films as double electrode layers separated by a chitosan electrolyte layer consisting of an ionic liquid. By taking advantage of the special hierarchical structure and the outstanding electrical and mechanical properties of the SWNT film electrodes, our actuators show orders-of-magnitude improvements in many aspects compared to previous ionic electroactive polymer (i-EAP) actuators, including superfast response (19 ms), quite wide available frequency range (dozens to hundreds of Hz), incredible large stress generating rate (1080 MPa/s), and ultrahigh mechanical output power density (244 W/kg). These remarkable achievements together with their facile fabrication, low driving voltage, flexibility, and long durability enable the SWNT-based actuators many applications such as artificial muscles for biomimetic flying insects or robots and flexible deployable reflectors.

Synthesis of large-scale periodic ZnO nanorod arrays and its blue-shift of UV luminescence

We demonstrate a promising route to fabricate large scale hexagonally patterned, vertically aligned ZnO nanorod arrays with small diameter. By adding 3-mercaptopropyltriethoxysilane (MPTES) molecules as a connection between catalyst and substrate the large size dispersion resulting from the removal of catalyst pattern is avoided, thus the catalyst particle pattern with tiny size dispersion and regular shape is obtained; the size can be tuned in a large range from 50 nm to 300 nm. Using this technique, ZnO nanorod arrays with tunable spacings and diameters are achieved, which also have uniform shape and length, good crystal quality, and vertical alignment on the substrate. Moreover, a pronounced blue-shift of ultraviolet (UV) luminescence spectra of ZnO nanorods with their diameters decreasing is observed. Combining the temperature-dependent photoluminescence (PL), we suggest that a materially decreased exciton-phonon interaction with the reduced diameter of ZnO nanorods is the main reason for the blue-shift of UV luminescence.

High performance, freestanding and superthin carbon nanotube/epoxy nanocomposite films

We develop a facile, effective and filter free infiltration method to fabricate high performance, freestanding and superthin epoxy nanocomposite films with directly synthesized Sing-Walled Carbon Nanotubes (SWNTs) film as reinforcement skeleton. It is found that the thicknesses of the nanocomposite films can be easily controlled in the range of 0.5-3 μm by dripping target amount of acetone diluted epoxy through the skeleton film. The consequent measurements reveal that the mechanical and electrical properties of SWNTs/epoxy nanocomposite films could be tailored in a quite wide range. For examples, the Youngs modulus of nanocomposite films can be tuned from 10 to 30 GPa, and the electrical conductivity can be ranged from 1000 S·cm(-1) to be insulated. Moreover, high load transfer efficiency in the nanocomposite films is demonstrated by the measured ultrahigh Raman bands shift rate (-30 ± 5 cm(-1)/% strain) under strain. The high effective modulus is derived as 774 ± 70 GPa for SWNTs inside this nanocomposite film.

Surface modification effect on photoluminescence of individual ZnO nanorods with different diameters

Optical properties of Al2O3 coated individual ZnO nanorods (NRs) with different diameters were studied by confocal micro-photoluminescence spectroscopy. The one-dimensional ZnO/Al2O3 core-shell NRs showed enhanced near band-edge emission compared with the same ZnO NRs before Al2O3 coating at room temperature. Besides, the relative intensity of the deep-level emission with respect to the near band-edge emission was reduced. A model was proposed to explain these spectral changes. For ZnO NRs with diameters above 360 nm, a multi-mode behavior resulting from whispering gallery resonance was observed. In addition, selective enhancement or quenching of different whispering gallery modes in ultraviolet (UV) emission was observed after Al2O3 coating at room temperature, which is due to the larger refractive index of Al2O3 compared with air. We proposed a model to explain these spectral changes as well. By comparing the optical properties before and after surface coating, our results suggest that surface coating of an Al2O3 layer is an effective way to tailor the optical properties of ZnO NRs.

Molecular surface structural changes of plasticized PVC materials after plasma treatment.

In this research, a variety of analytical techniques including sum frequency generation vibrational spectroscopy (SFG), coherent anti-Stokes Raman spectroscopy (CARS), and X-ray photoelectron spectroscopy (XPS) have been employed to investigate the surface and bulk structures of phthalate plasticized poly(vinyl chloride) (PVC) at the molecular level. Two types of phthalate molecules with different chain lengths, diethyl phthalate (DEP) and dibutyl phthalate (DBP), mixed with PVC in various weight ratios were examined to verify their different surface and bulk behaviors. The effects of oxygen and argon plasma treatment on PVC/DBP and PVC/DEP hybrid films were investigated on both the surface and bulk of films using SFG and CARS to evaluate the different plasticizer migration processes. Without plasma treatment, SFG results indicated that more plasticizers segregate to the surface at higher plasticizer bulk concentrations. SFG studies also demonstrated the presence of phthalates on the surface even at very low bulk concentration (5 wt %). Additionally, the results gathered from SFG, CARS, and XPS experiments suggested that the PVC/DEP system was unstable, and DEP molecules could leach out from the PVC under low vacuum after several minutes. In contrast, the PVC/DBP system was more stable; the migration process of DBP out of PVC could be effectively suppressed after oxygen plasma treatment. XPS results indicated the increase of C═O/C-O groups and decrease of C-Cl functionalities on the polymer surface after oxygen plasma treatment. The XPS results also suggested that exposure to argon plasma induced chemical bond breaking and formation of cross-linking or unsaturated groups with chain scission on the surface. Finally, our results indicate the potential risk of using DEP molecules in PVC since DEP can easily leach out from the polymeric bulk.

Observing Phthalate Leaching from Plasticized Polymer Films at the Molecular Level

Phthalates, the most widely used plasticizers in poly(vinyl chloride) (PVC), have been extensively studied. In this paper, a highly sensitive, easy, and effective method was developed to examine short-term phthalate leaching from PVC/phthalate films at the molecular level using sum frequency generation vibrational spectroscopy (SFG). Combining SFG and Fourier transform infrared spectroscopy (FTIR), surface and bulk molecular structures of PVC/phthalate films were also comprehensively evaluated during the phthalate leaching process under various environments. The leaching processes of two phthalates, diethyl phthalate (DEP) and dibutyl phthalate (DBP), from the PVC/phthalate films with various weight ratios were studied. Oxygen plasma was applied to treat the PVC/phthalate film surfaces to verify its efficacy on preventing/reducing phthalate leaching from PVC. Our results show that DBP is more stable than DEP in PVC/phthalate films. Even so, DBP molecules were still found to very slowly leach to the environment from PVC at 30 °C, at a rate much slower than DEP. Also, the bulk DBP content substantially influences the DBP leaching. Higher DBP bulk concentration yields less stable DBP molecules in the PVC matrix, allowing molecules to leach from the polymer film more easily. Additionally, DBP leaching is very sensitive to temperature changes; higher temperature can strongly enhance the leaching process. For most cases, the oxygen plasma treatment can effectively prevent phthalate leaching from PVC films (e.g., for samples with low bulk concentrations of DBP-5 and 30 wt %). It is also capable of reducing phthalate leaching from high DBP bulk concentration PVC samples (e.g., 70 wt % DBP in PVC/DBP mixture). This research develops a highly sensitive method to detect chemicals at the molecular level as well as provides surface and bulk molecular structural changes. The method developed here is general and can be applied to detect small amounts of chemical/biological environmental contaminants.

Controlled Drug Release and Hydrolysis Mechanism of Polymer–Magnetic Nanoparticle Composite

Uniform and multifunctional poly(lactic acid) (PLA)-nanoparticle composite has enormous potential for applications in biomedical and materials science. A detailed understanding of the surface and interface chemistry of these composites is essential to design such materials with optimized function. Herein, we designed and investigated a simple PLA-magnetic nanoparticle composite system to elucidate the impact of nanoparticles on the degradation of polymer-nanoparticle composites. In order to have an in-depth understanding of the mechanisms of hydrolysis in PLA-nanoparticle composites, degradation processes were monitored by several surface sensitive techniques, including scanning electron microscopy, contact angle goniometry, atomic force microscopy, and sum frequency generation spectroscopy. As a second-order nonlinear optical technique, SFG spectroscopy was introduced to directly probe in situ chemical nature at the PLA-magnetic nanoparticle composite/aqueous interface, which allowed for the delineation of molecular mechanisms of various hydrolysis processes for degradation at the molecular level. The best PLA-NP material, with a concentration of 20% MNP in the composite, was found to enhance the drug release rate greater than 200 times while maintaining excellent controlled drug release characteristics. It was also found that during hydrolysis, various crystalline-like PLA domains on the surfaces of PLA-nanoparticle composites influenced various hydrolysis behaviors of PLA. Results from this study provide new insight into the design of nanomaterials with controlled degradation and drug release properties, and the underlined molecular mechanisms. The methodology developed in this study to characterize the polymer-nanoparticle composites is general and widely applicable.

In situ observation of water behavior at the surface and buried interface of a low-k dielectric film.

Water adsorption in porous low-k dielectrics has become a significant challenge for both back-end-of-line integration and reliability. A simple method is proposed here to achieve in situ observation of water structure and water-induced structure changes at the poly(methyl silsesquioxane) (PMSQ) surface and the PMSQ/solid buried interface at the molecular level by combining sum frequency generation (SFG) vibrational spectroscopic and Fourier transform infrared (FTIR) spectroscopic studies. First, in situ SFG investigations of water uptake were performed to provide direct evidence that water diffuses predominantly along the PMSQ/solid interface rather than through the bulk. Furthermore, SFG experiments were conducted at the PMSQ/water interface to simulate water behavior at the pore inner surfaces for porous low-k materials. Water molecules were found to form strong hydrogen bonds at the PMSQ surface, while weak hydrogen bonding was observed in the bulk. However, both strongly and weakly hydrogen bonded water components were detected at the PMSQ/SiO2 buried interface. This suggests that the water structures at PMSQ/solid buried interfaces are also affected by the nature of solid substrate. Moreover, the orientation of the Si-CH3 groups at the buried interface was permanently changed by water adsorption, which might due to low flexibility of Si-CH3 groups at the buried interface. In brief, this study provides direct evidence that water molecules tend to strongly bond (chemisorbed) with low-k dielectric at pore inner surfaces and at the low-k/solid interface of porous low-k dielectrics. Therefore, water components at the surfaces, rather than the bulk, are likely more responsible for chemisorbed water related degradation of the interconnection layer. Although the method developed here was based on a model system study, we believe it should be applicable to a wide variety of low-k materials.

In situ comprehensive characterization of optoelectronic nanomaterials for device purposes

We have combined optical fiber probe and nanoprobe techniques in a scanning electron microscope, which enables in situ optical, electrical and structural characterization of optoelectronic nanomaterials and nanodevices. The nanoprobe technique, employing sharp metal tips, is used for in situ nano-manipulation, contact and electrical measurement. The fiber probe, coupled to a spectrometer or a laser and controlled by a nano-manipulator, allows local optical detection or excitation. We show in situ assembly of a light emitter and photodetector based on individual nanostructures, demonstrating the potential application of the above technique in building prototype optoelectronic devices and selecting suitable nanostructures for device purposes. In addition, the angular resolving power of the fiber probe detection is demonstrated to be useful for studying nanoscale waveguides.

Effect of Solvent on Surface Ordering of Poly(3-hexylthiophene) Thin Films

Enhancement of charge transport in organic polymer semiconductors is a crucial step in developing optimized devices. A variety of sample preparation conditions, such as film fabrication method, solvent species, and annealing, were found to influence the hole mobility of organic polymers. Despite the fact that many factors can influence their performance, it is believed that polymer surface ordering plays a key role in determining organic polymer function. Here, sum frequency generation (SFG) vibrational spectroscopy was used to nondestructively map the surface/interfacial ordering of poly(3-hexylthiophene) (P3HT) films prepared using different solvents; we believe that solvent interactions determine the degree of surface/interfacial ordering. Both X-ray diffraction (XRD) spectroscopy and scanning electron microscopy (SEM) were used to supplement SFG to systematically study bulk crystallinity and surface morphology. We conclude that SFG is a powerful tool to elucidate the surface/interfacial structural information on polymer semiconducting films. We demonstrate that the solvent composition used to prepare P3HT thin films influences the resulting film surface morphology, surface/interfacial ordering, and bulk crystallinity.