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High heterogeneity in the membrane protein expression of small extracellular vesicles (sEVs) means that bulk methods relying on antibody-based capture for expression analysis have a drawback that each type of antibody may capture a different sub-population. An improved approach is to capture a representative sEV population, without any bias, and then perform a multiplexed protein expression analysis on this population. However, such a possibility has been largely limited to fluorescence-based methods. Here, we present a novel electrostatic labelling strategy and a microchip-based all-electric method for membrane protein analysis of sEVs. The method allows us to profile multiple surface proteins on the captured sEVs using alternating charge labels. It also permits the comparison of expression levels in different sEV-subtypes. The proof of concept was tested by capturing sEVs both non-specifically (unbiased) as well as via anti-CD9 capture probes (biased), and then profiling the expression levels of various surface proteins using the charge labelled antibodies. The method is the first of its kind, demonstrating an all-electrical and microchip based method that allows for unbiased analysis of sEV membrane protein expression, comparison of expression levels in different sEV subsets, and fractional estimation of different sEV sub-populations. These results were also validated in parallel using a single-sEV fluorescence technique.

Precision cancer medicine have changed the treatment landscape of non-small cell lung cancer (NSCLC) as illustrated by tyrosine kinase inhibitors (TKIs) towards mutated Epidermal growth factor receptor (EGFR). Yet, responses to such TKIs e.g., erlotinib and osimertinib among patients are heterogenous and there is a need for non-invasive blood-based analytics to follow treatment response and reveal resistance to improve patient’s treatment outcome. Recently, extracellular vesicles (EVs) have been identified as an important source of tumor biomarkers promising to revolutionize liquid biopsy-based diagnosis of cancer. However, high heterogeneity has been a major bottleneck. The pathological signature is often hidden in the differential expression of membrane proteins in a subset of EVs which are difficult to identify with bulk techniques. Using a fluorescence-based approach, we for the first time demonstrate that the single-EV technique can be used to monitor the treatment response of targeted cancer therapies such as TKIs towards EGFR. To test the hypothesis, we analyzed the membrane proteins of native EVs extracted from EGFR-mutant NSCLC cell line, both prior and post treatment with EGFR-TKIs erlotinib or osimertinib. The selected cell line being refractory to erlotinib and responsive to osimertinib makes it a suitable model system. The expression level of five surface proteins; two common tetraspanins (CD9, CD81) and three markers of specific interest in lung cancer (EGFR, PD-L1, HER2) were studied. The data suggest that in contrast to erlotinib, the osimertinib treatment increases the population of PD-L1, EGFR and HER2 positive EVs while the expression level per EV decreases for all the three markers. The PD-L1 and HER2 expressing EV population seems to increase by several fold because of osimertinib treatment. The observations agree with the previous reports performed on cellular level indicating the biomarker potential of EVs for liquid-biopsy based monitoring of targeted cancer treatments.HighlightsMembrane protein analyses of single EVs may reveal distinct differences when lung cancer cells are refractory vs responsive under different EGFR-TKI treatments.Comparison of 1stgeneration erlotinib and 3rdgeneration osimertinib shows clear signature on the expression of PD-L1, EGFR, HER2 on single EVsColocalization showed a change in common marker combinations before after treatment.PD-L1 expression per vesicle decreases while the number of PD-L1 positive EVs increases as a result of osimertinib treatment, indicating that such signature may not be detectable under bulk analysis

Precision cancer medicine has changed the treatment landscape of non-small cell lung cancer (NSCLC) as illustrated by the introduction of tyrosine kinase inhibitors (TKIs) towards mutated epidermal growth factor receptor (EGFR). However, as responses to EGFR-TKIs are heterogenous among NSCLC patients, there is a need for ways to early monitor changes in treatment response in a non-invasive way e.g., in patient's blood samples. Recently, extracellular vesicles (EVs) have been identified as a source of tumor biomarkers which could improve on non-invasive liquid biopsy-based diagnosis of cancer. However, the heterogeneity in EVs is high. Putative biomarker candidates may be hidden in the differential expression of membrane proteins in a subset of EVs hard to identify using bulk techniques. Using a fluorescence-based approach, we demonstrate that a single-EV tech-nique can detect alterations in EV surface protein profiles. We analyzed EVs isolated from an EGFR-mutant NSCLC cell line, which is refractory to EGFR-TKIs erlotinib and responsive to osimertinib, before and after treatment with these drugs and after cisplatin chemotherapy. We studied expression level of five proteins; two tetraspanins (CD9, CD81), and three markers of interest in lung cancer (EGFR, programmed death-ligand 1 (PD-L1), human epidermal growth factor receptor 2 (HER2)). The data reveal alterations induced by the osimertinib treatment compared to the other two treatments. These include the growth of the PD-L1/HER2-positive EV population, with the largest increase in vesicles exclusively expressing one of the two proteins. The expression level per EV decreased for these markers. On the other hand, both the TKIs had a similar effect on the EGFR-positive EV population.

In this study, we demonstrate the fabrication, characterization, and application of a microchip-based electrokinetic biosensor which exploits streaming current for signal transduction. The sensor chips, fabricated using standard silicon fabrication techniques, are based on Si-glass microfluidics offering precision, robustness, and transparency. A custom-built chip-manifold allowing easy interfacing with standard microfluidic connections is also developed which shows leak-free integration of the microchips up to 6 bar of applied pressure. Within this range of pressure, the devices show linear and highly reproducible values for flow rates and streaming current with RMS noise below 20 pA. The microchips designed for multiplexed measurements were tested with the detection of free proteins (streptavidin) and also transmembrane proteins of small extracellular vesicles (sEVs) to demonstrate the capacity of the microchips to detect various types of bio-analytes. The limit of detection (LOD) for streptavidin was estimated to be 0.5 nM while for the transmembrane protein (CD9), the LOD was found to be 1.2×106 sEVs/mL. The sensitivity (LOD) of the devices was found to be about 4 times better in targeting CD9 transmembrane protein of H1975 extracellular vesicles when compared to commercial silica capillary which was used previously. The improvement in LOD is attributed to the higher surface quality of the sensor in terms of the density of surface charges which may be further exploited for even lower LOD. In addition, optical detection of fluorophore-tagged standard proteins was done through the optical window of the chip manifold and the transparent glass cap of the microchip.

Liquid biopsies based on extracellular vesicle (EV) protein profiles represent a promising tool for treatment monitoring of tumors, including non-small-cell lung cancers (NSCLC). In this study, we present the development of an electrokinetic sensor for multiplexed surface protein profiling of EVs and analysis of clinical samples. The method detects the difference in the streaming current obtained as a result of EV binding to the inner surface of a functionalized microcapillary, thereby estimating the expression level of a surface marker. Using multiple microchannels functionalized with different antibodies in a parallel fluidic connection, we first demonstrate the capacity for simultaneous detection of multiple surface markers in small EVs (sEVs) from NSCLC cells. To investigate the prospects of liquid biopsies based on EVs, we then apply the method to profile sEVs isolated from the pleural effusion (PE) fluids of three NSCLC adenocarcinoma patients with different genomic alterations (ALK-fusion, KRAS and EGFR) and applied treatments (chemotherapy, EGFR or ALK tyrosine kinase inhibitors). These vesicles were targeted against CD9 tetraspanin, as well as EGFR and PD-L1, two markers of interest in NSCLC. The electrokinetic signals showed detection of these markers on sEVs yet highlighting distinct interpatient differences, e.g., increased EGFR levels in sEVs from a patient with EGFR mutation as compared to an ALK-mutant one. The sensors also detected differences in PD-L1 expressions, in line with those measured by complementary methods. The analysis of sEVs from a patient prior and post crizotinib treatment also revealed a significant increase in the expression of some markers, e.g. EGFR and PD-L1. The obtained results hold promise for the application of the method for tumor treatment monitoring based on sEVs from liquid biopsies.

Nanoscale extracellular vesicle (EVs) have been found to play a key role in intercellular communication, offering opportunities for both diagnostics and therapeutics. However, lying below the diffraction limit and also being highly heterogeneous in their size, morphology and abundance, these vesicles pose significant challenges for their physical characterization. Here, we present a direct visual approach for their accurate morphological and size-based profiling by using scanning electron microscopy (SEM). To achieve that, we methodically examined various process steps and developed a protocol to improve the throughput, conformity and image quality while preserving the shape of EVs. The investigation was performed with small EVs (sEVs) isolated from a non-small cell lung cancer (NSCLC) cell line H1975 as well as from a human serum, and the results were compared with those obtained from nanoparticle tracking analysis (NTA). While the comparison of the sEV size distributions showed good agreement between the two methods for large sEVs (diameter >70 nm), the microscopy based approach showed a better capacity for analyses on smaller vesicles, with higher sEV counts compared to NTA. In addition, we demonstrated the possibility of identifying non-EV particles based on size and morphological features. The study also showed process steps that can generate artifacts bearing resemblance with sEVs. The results therefore present a simple way to use a widely available microscopy tool for accurate and high throughput physical characterization of EVs.

Nanosized extracellular vesicles (EVs) have been found to play a key role in intercellular communication, offering opportunities for both disease diagnostics and therapeutics. However, lying below the diffraction limit and also being highly heterogeneous in their size, morphology and abundance, these vesicles pose significant challenges for physical characterization. Here, we present a direct visual approach for their accurate morphological and size-based profiling by using scanning electron microscopy (SEM). To achieve that, we methodically examined various process steps and developed a protocol to improve the throughput, conformity and image quality while preserving the shape of EVs. The study was performed with small EVs (sEVs) isolated from a non-small-cell lung cancer (NSCLC) cell line as well as from human serum, and the results were compared with those obtained from nanoparticle tracking analysis (NTA). While the comparison of the sEV size distributions showed good agreement between the two methods for large sEVs (diameter > 70 nm), the microscopy based approach showed a better capacity for analyses of smaller vesicles, with higher sEV counts compared to NTA. In addition, we demonstrated the possibility of identifying non-EV particles based on size and morphological features. The study also showed process steps that can generate artifacts bearing resemblance with sEVs. The results therefore present a simple way to use a widely available microscopy tool for accurate and high throughput physical characterization of EVs.

An electrical immuno-sandwich assay utilizing an electrokinetic-based streaming current method for signal transduction is proposed. The method records the changes in streaming current, first when a target molecule binds to the capture probes immobilized on the inner surface of a silica micro-capillary, and then when the detection probes interact with the bound target molecules on the surface. The difference in signals in these two steps constitute the response of the assay, which offers better target selectivity and a linear concentration dependent response for a target concentration within the range 0.2–100 nM. The proof of concept is demonstrated by detecting different concentrations of Immunoglobulin G (IgG) in both phosphate buffered saline (PBS) and spiked in E. coli cell lysate. A superior target specificity for the sandwich assay compared to the corresponding direct assay is demonstrated along with a limit of detection of 90 pM in PBS. The prospect of improving the detection sensitivity was theoretically analysed, which indicated that the charge contrast between the target and the detection probe plays a crucial role in determining the signal. This aspect was then experimentally validated by modulating the zeta potential of the detection probe by conjugating negatively charged DNA oligonucleotides. The length of the conjugated DNA was varied from 5 to 30 nucleotides, altering the zeta potential of the detection probe from −9.3 ± 0.8 mV to −20.1 ± 0.9 mV. The measurements showed a clear and consistent enhancement of detection signal as a function of DNA lengths. The results presented here conclusively demonstrate the role of electric charge in detection sensitivity as well as the prospect for further improvement. The study therefore is a step forward in developing highly selective and sensitive electrokinetic assays for possible application in clinical investigations.

Being a key player in intercellular communications, nanoscale extracellular vesicles (EVs) offer unique opportunities for both diagnostics and therapeutics. However, their cellular origin and functional identity remain elusive due to the high heterogeneity in their molecular and physical features. Here, for the first time, multiple EV parameters involving membrane protein composition, size and mechanical properties on single small EVs (sEVs) are simultaneously studied by combined fluorescence and atomic force microscopy. Furthermore, their correlation and heterogeneity in different cellular sources are investigated. The study, performed on sEVs derived from Human Embryonic Kidney 293, Cord Blood Mesenchymal Stromal and Human Acute Monocytic Leukemia cell lines, identifies both common and cell line-specific sEV subpopulations bearing distinct distributions of the common tetraspanins (CD9, CD63 and CD81) and biophysical properties. Although the tetraspanin abundances of individual sEVs are independent of their sizes, the expression levels of CD9 and CD63 are strongly correlated. A sEV population co-expressing all the three tetraspanins in relatively high abundance, however, having on average diameters

Liquid biopsies based on extracellular vesicles (EVs) represent a promising tool for treatment monitoring of tumors, including non-small-cell lung cancers (NSCLC). In this study, we report on a multiplexed electrokinetic sensor for surface protein profiling of EVs from clinical samples. The method detects the difference in the streaming current generated by EV binding to the surface of a functionalized microcapillary, thereby estimating the expression level of a marker. Using multiple microchannels functionalized with different antibodies in a parallel fluidic connection, we first demonstrate the capacity for simultaneous detection of multiple surface markers in small EVs (sEVs) from NSCLC cells. To investigate the prospects of liquid biopsies based on EVs, we then apply the method to profile sEVs isolated from the pleural effusion (PE) fluids of five NSCLC patients with different genomic alterations (ALK, KRAS or EGFR) and applied treatments (chemotherapy, EGFR- or ALK-tyrosine kinase inhibitors). The vesicles were targeted against CD9, as well as EGFR and PD-L1, two treatment targets in NSCLC. The electrokinetic signals show detection of these markers on sEVs, highlighting distinct interpatient differences, e.g., increased EGFR levels in sEVs from a patient with EGFR mutation as compared to an ALK-fusion one. The sensors also detect differences in PD-L1 expressions. The analysis of sEVs from a patient prior and post ALK-TKI crizotinib treatment reveals significant increases in the expressions of some markers (EGFR and PD-L1). These results hold promise for the application of the method for tumor treatment monitoring based on sEVs from patient liquid biopsies.

We present an approach to improve the detection sensitivity of a streaming current-based biosensor for membrane protein profiling of small extracellular vesicles (sEVs). The experimental approach, supported by theoretical investigation, exploits electrostatic charge contrast between the sensor surface and target analytes to enhance the detection sensitivity. We first demonstrate the feasibility of the approach using different chemical functionalization schemes to modulate the zeta potential of the sensor surface in a range -16.0 to -32.8 mV. Thereafter, we examine the sensitivity of the sensor surface across this range of zeta potential to determine the optimal functionalization scheme. The limit of detection (LOD) varied by 2 orders of magnitude across this range, reaching a value of 4.9 x 10(6) particles/mL for the best performing surface for CD9. We then used the optimized surface to profile CD9, EGFR, and PD-L1 surface proteins of sEVs derived from non-small cell lung cancer (NSCLC) cell-line H1975, before and after treatment with EGFR tyrosine kinase inhibitors, as well as sEVs derived from pleural effusion fluid of NSCLC adenocarcinoma patients. Our results show the feasibility to monitor CD9, EGFR, and PD-L1 expression on the sEV surface, illustrating a good prospect of the method for clinical application.

Small extracellular vesicles (sEVs) generated from the endolysosomal system, often referred to as exosomes, have attracted interest as a suitable biomarker for cancer diagnostics, as they carry valuable biological information and reflect their cells of origin. Herein, we propose a simple and inexpensive electrical method for label-free detection and profiling of sEVs in the size range of exosomes. The detection method is based on the electrokinetic principle, where the change in the streaming current is monitored as the surface markers of the sEVs interact with the affinity reagents immobilized on the inner surface of a silica microcapillary. As a proof-of-concept, we detected sEVs derived from the non-small-cell lung cancer (NSCLC) cell line H1975 for a set of representative surface markers, such as epidermal growth factor receptor (EGFR), CD9, and CD63. The detection sensitivity was estimated to be ∼175000 sEVs, which represents a sensor surface coverage of only 0.04%. We further validated the ability of the sensor to measure the expression level of a membrane protein by using sEVs displaying artificially altered expressions of EGFR and CD63, which were derived from NSCLC and human embryonic kidney (HEK) 293T cells, respectively. The analysis revealed that the changes in EGFR and CD63 expressions in sEVs can be detected with a sensitivity in the order of 10% and 3%, respectively, of their parental cell expressions. The method can be easily parallelized and combined with existing microfluidic-based EV isolation technologies, allowing for rapid detection and monitoring of sEVs for cancer diagnosis.

Using the electrokinetic principle, we demonstrate a novel approach to modulate the response of an ion sensitive silicon-nanoribbon field-effect-transistor, effectively manipulating the device sens ...

Electrokinetic principles such as streaming current and streaming potential are extensively used for surface characterization. Recently, they have also been used in biosensors, resulting in enhanced sensitivity and simpler device architecture. Theoretical models regarding streaming current/potential studies of particle-covered surfaces have identified features such as the particle size, shape and surface charge to influence the electrokinetic signals and consequently, the sensitivity and effective operational regime of the biosensor. By using a set of well-characterized proteins with varying size and net surface charge, this article experimentally verifies the theoretical predictions about their influence on the sensor signal. Increasing protein size was shown to enhance the signal when their net surface charge was either opposite to that of the sensor surface, or close to zero, in agreement with the theoretical predictions. However, the effect gradually saturated as the protein size exceeded the coulomb screening length of the electrolyte. In contrast, the proteins containing the same type of charge as the surface showed little or no difference, except that the signal inverted. The magnitude of the surface charge was also shown to influence the signal. The sensitivity of the technique for protein detection varied over two orders of magnitude, depending upon the size and surface charge. Furthermore, the capacity of the electrokinetic method for direct electrical detection of various proteins, including those carrying little or no net electric charges, is demonstrated.

A novel interfacial energy driven colloidal lithography technique to fabricate periodic patterns from solution-phase is presented and the feasibility and versatility of the technique is demonstrate ...

Nanosized octagonal pyramidal frusta of indium phosphide were selectively grown at circular hole openings on a silicon dioxide mask deposited on indium phosphide and indium phosphide pre-coated silicon substrates. The eight facets of the frusta were determined to be {111} and {110} truncated by a top (100) facet. The size of the top flat surface can be controlled by the diameter of the openings in the mask and the separation between them. The limited height of the frusta is attributed to kinetically controlled selective growth on the (100) top surface. Independent analyses with photoluminescence, cathodoluminescence and scanning spreading resistance measurements confirm certain doping enrichment in the frustum facets. This is understood to be due to crystallographic orientation dependent dopant incorporation. The blue shift from the respective spectra is the result of this enrichment exhibiting the Burstein–Moss effect. Very bright panchromatic cathodoluminescence images indicate that the top surfaces of the frusta are free from dislocations. The good optical and morphological quality of the nanopyramidal frusta indicates that the fabrication method is very attractive for the growth of site-, shape-, and number-controlled semiconductor quantum dot structures on silicon for nanophotonic applications.

We present a simple and inexpensive method for label-free detection of biomolecules. The method monitors the changes in streaming current in a fused silica capillary as target biomolecules bind to immobilized receptors on the inner surface of the capillary. To validate the concept, we show detection and time response of different protein-ligand and protein-protein systems: biotin-avidin and biotin-streptavidin, barstar-dibarnase and Z domain-immunoglobulin G (IgG). We show that specific binding of these biomolecules can be reliably monitored using a very simple setup. Using sequential injections of various proteins at a diverse concentration range and as well as diluted human serum we further investigate the capacity of the proposed technique to perform specific target detection from a complex sample. We also investigate the time for the signal to reach equilibrium and its dependence on analyte concentration and demonstrate that the current setup can be used to detect biomolecules at a concentration as low as 100pM without requiring any advanced device fabrication procedures. Finally, an analytical model based on diffusion theory has been presented to explain the dependence of the saturation time on the analyte concentration and capillary dimensions and how reducing length and inner diameter of the capillary is predicted to give faster detection and in practice also lower limit of detection.

ZnO nanowire arrays were functionalized with colloidal CdSe quantum dots stabilized by 3-mercaptopropionic acid to form hybrid devices. The photoconductivity of the nanowire/quantum-dot devices was studied under selective photoexcitation of the quantum dots, and it was found that the dynamics strongly depend on the gas environment. Desorption of surface oxygen from both the ZnO nanowires and the CdSe quantum dots, activated by electron tunnelling between the nanowires and the quantum dots, is found to be the dominating process that determines the dynamics of the photoconductivity in the hybrid nanowire/quantum-dot devices.

This paper discusses different aspects of optical applications of ZnO nanowires NWs. After a description of the relevant synthesis and fabrication techniques, light-emitting diodes based on ZnO NW and NW arrays are introduced and different experimental realizations from the literature are discussed. The working principle of ZnO UV photodetectors is presented, and improvements and limitations of ZnO- NW-based dye-sensitized solar cells are discussed. Different aspects of ZnO-NW waveguides and their potential application for biological sensing are described. Finally, the current status of ZnO-NW-based UV lasers is presented.

This review demonstrates that ion irradiation is a very useful tool in order to tailor the properties of semiconductor nanowires. Besides optical and electrical doping provided by adequate ion species and ion energies, one can use ion beams also for the controlled shaping of the morphology of nanostructures. Here, one utilizes the commonly as 'negative' described characteristics of ion implantation: defect formation and sputtering. We show that ion beams can be even used for an alignment of the nanowires. Furthermore, we report here on several successful experiments in order to modify the electrical and optical properties in a controlled manner of ZnO semiconductor nanowires by the use of transition metals, rare earth elements and hydrogen ions.

This paper discusses the surface effects and nonlinear optical properties of ZnO nanowires. First, the influence of the large surface-to-volume ratio of the nanowires on their photoluminescence properties is shown. The occurrence of a surface-exciton emission line is demonstrated and its properties are studied in time-integrated and time-resolved photoluminescence measurements. It is further demonstrated that this band is sensitive to surface modifications of the nanowires, such as dielectric and metallic coatings. It is shown that hydrogen can passivate deep defects in ZnO nanowires thereby reducing the defect luminescence and strongly enhancing the near-bandedge excitonic luminescence. The photoluminescence properties of chemically synthesized ZnO nanowires are compared to those of nanowires grown by vapor-transport techniques. The non-linear coefficients of chemically synthesized nanowires are analyzed, and first preliminary measurements of the optical gain of a ZnO nanowire waveguide are analyzed.

A unique strategy for effective, versatile, and facile surface biofunctionalization employing a recombinant spider silk protein genetically functionalized with the antibody-binding Z domain (Z-4Rep ...

We report on room temperature electroluminescence from an inorganic/organic heterojunction light emitting diode based on ZnO nanowire arrays. The heterojunction is fabricated by depositing the p-type polymer poly(3,4 ethylenedioxythiophene) : p o l y(st y renesulfonate) (PEDOT:PSS) on n-type ZnO nanowires grown by electrodeposition on transparent conducting glass (ITO) substrates. The nanowires are encapsulated in a thin polystyrene film deposited from high-molecular-weight solution. Electron injection occurs through the transparent ITO layer while hole injection is mediated by the PEDOT layer and gold contacts. The current-voltage (I-V) characteristics of the device shows a diode-like behavior. A broad emission spectrum covering most of the visible range and reaching to the near ultraviolet is observed at voltages between 6 and 8 V under ambient condition. The device operation is stable for more than 5 h.

Hierarchical nano/micro structures of ZnO have been fabricated by solvothermal approach on sol–gel derived ZnO thin films. Paintbrush like nano/micro rod assembly, double-sided brush and windmill type architectures of ZnO are obtained when the ZnO thin film coated substrates were treated solvothermally in water at pH 10. Aligned nanorods are obtained at pH ∼ 13.5 in water. In ethylenediamine-water solvent divergent micro/nanorod assemblies such as hemispherical dandelion, rice plant type bush of ZnO are obtained. Increase in the percentage of ethyelendiamine resulted in the formation of smaller assemblies of relatively thin nanorods. Initial slow reaction caused by the slow increase of the temperature inside the reaction medium and the different growth kinetics of the ZnO crystals are supposed to be the reason behind the architectural assemblies of the ZnO crystals.

ZnO is one of the most important semiconductors having a wide variety of applications in photonic, field emission and sensing devices. In addition, it exhibits a wide variety of morphologies in the nano regime that can be grown by tuning the growth habit of the ZnO crystal. Among various nanostructures, oriented 1-D nanoforms are particularly important for applications such as UV laser, sensors, UV LED, field emission displays, piezoelectric nanogenerator etc. We have developed a soft chemical approach to fabricate well-aligned arrays of various 1-D nanoforms like nanonails, nanowires and nanorods. The microstructural and photoluminescence properties of all the structures were investigated and tuned by varying the synthesis parameters. Field emission study from the aligned nanorod arrays exhibited high current density and a low turn-on field. These arrays also exhibited very strong UV emission and week defect emission. These structures can be utilized to fabricate efficient UV LEDs.

ZnO nanocrystals with various morphologies such as nanorod arrays, flower like assemblies, spherical particles, hexagonal cones, and self assembled microstructures were prepared by a solvothermal approach. It was observed that morphology of the ZnO nanostructures were very much solvent dependent in solvothermal approach. Water, ethylenediamine, and ethylene glycol-water mixture favors the formation of nanorods. Flower like assemblies of ZnO were produced in benzene. Spherical as well as cone like nanoparticles and their assemblies were produced in ethylene glycol. The ZnO nanostructures were characterized by X-ray diffraction, scanning and transmission electron microscopy, and photoluminescence studies.

In this paper, we report the preparation of vertically aligned ZnO−ZnS core−shell and ZnS nanorod arrays with crystallographic orientation along the c-axis by sulfidation of aligned ZnO nanorod arrays. The ZnO nanorod arrays were prepared by a surfactant assisted soft chemical method on a sol−gel derived ZnO thin film. Partial conversion of the ZnO nanorod surface to ZnS at 400 °C in an H2S and argon gas mixture produces ZnO−ZnS core−shell structures, whereas the complete conversion at 600 °C produces well-aligned ZnS nanorods. The influence of the sulfidation time and annealing temperature on the conversion of ZnO nanorods to ZnO−ZnS core−shell nanorods is investigated. TEM studies revealed that the sulfidation process begins at the surface of the ZnO nanorods, which gradually increase inward, retaining the morphology and following the crystal orientation of the ZnO core. The nanostructures showed enhanced UV emission properties. The described procedures open a way to convert a microstructured material i...

Crystalline SnS wires of micro- and nanometer scale have been synthesized over tin metal foils at room temperature using a simple surfactant-assisted approach. Scanning electron microscopy, transmission electron microscopy, UV−Vis−near infrared (NIR) and Fourier transform infrared (FTIR) spectroscopy were used to characterize the SnS nanowires. X-ray diffraction (XRD) analysis confirmed the formation of the pure orthorhombic phase of SnS. The optical band gap of the samples was found to be ∼1.4 eV. From the investigation, the formation of nanowires could be explained in two steps: initial cracking/splitting of the nanoflakes was followed by a top-growth mechanism to form ultralong nanowires. Effects of various experimental parameters on the growth mechanism were investigated. Present studies have shown that this facile process also can be extended for the synthesis of other low dimensional structures.

Anisotropic growth of ZnO nanorod arrays on ZnO thin films was achieved at a temperature of 90 degrees C by a surfactant-assisted soft chemical approach with control over size and orientation. ZnO thin films with c-axis preferred orientation had been achieved by the sol-gel technique. Lengths, diameters, and the degree of alignment of the ZnO nanorods were controlled by changing the experimental parameters. It was observed that the surfactant was essential to restrict the lateral growth of the nanorods, whereas the pH level of the reaction medium controlled the length of the nanorods. On the other hand, the orientation of the nanorods depended on the crystalline orientation of the film as well as the pH of the reaction medium. Room-temperature photoluminescence studies revealed that the ZnO nanorods with the best alignment exhibited the best emission property. The ZnO nanorods exhibited a strong UV emission peak at approximately 3.22 eV, ascribed to the band-edge emission. The field emission studies of the well-aligned nanorod arrays exhibited a low turn-on field of 1.7 V/microm to get an emission current density of 0.1 microA/cm(2).

Mg0.05Zn0.95O/SiO2 nanocomposite films in the molar ratio 25:75 consisting of Mg0.05Zn0.95O nanoparticles embedded in a dielectric matrix were prepared by sol–gel technique (spin coating). Optical transmittance, Raman effect and photoluminescence measurements of the composites indicated effective capping of the Mg0.05Zn0.95O nanoparticles (radii 1. 61–1.68 nm) in the host showing practically no variation of particle size with the post deposition annealing treatments. The blue shift of the band gap (4.29–4.23 eV) from that of bulk Mg0.05Zn0.95O indicated strong carrier confinement for samples annealed at T ≤ 873 K. Highly intense UV emission ( ∼ 4.14 eV) compared to that of defect related emission (2.59 eV) at room temperature was obtained by incorporating 5% Mg in ZnO.

Well-crystallized Mg x Zn 1-x O films were deposited on quartz substrates by sol-gel technique with a variation of x value from 0 to 0.15. The samples were annealed at different temperatures (500 °C to 700 °C) in air and oxygen atmosphere to study the effect of annealing atmosphere on the luminescence properties of the films. The optical, microstructural and photoluminescence properties of the films were studied. It was found that the band gap of the films increased with increasing Mg concentration (x value). A remarkable change in the photoluminescence spectra of the films for x = 0.05 was observed by varying the annealing atmosphere. Highly intense UV emission at room temperature could be obtained by annealing the Mg 0.05 Z 0.95 O film in static oxygen atmosphere, while the intensity of the visible defect related luminescence could be reduced, resulting in a high intensity ratio (∼100) of the two.

This article describes the design and fabrication of hierarchical nanomicrostructured polymer surfaces with high hydrophobicity. The nanoscale roughness is achieved by stamping a ZnO nanowire film into PDMS. Subsequently, microstructures with different periodicities are created in the stamped PDMS sample by direct laser writing using femtosecond pulses. With this approach, we were able to produce hierarchical surface morphologies, composed of nano and microscale structures that exhibit water contact angles larger than 160 degrees.

We report on low-temperature photoluminescence studies of ZnO nanowires coated with thin metallic films. For all analyzed metals (Al, In, Au, Ni, Cu), we find an increased relative intensity of the green deep-level emission. This is accompanied by a significant reduction of the relative intensity of the surface exciton band. The observed effects are most likely related to the formation of metal induced gap states in the surface region of the ZnO nanowires. A model for the band structure in the surface region of the metal-coated nanowires is proposed that successfully explains the changes in the photoluminescence spectra after the coating process. (© 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)

We present an approach to fabricate ZnO nanowires/polymer composite into three-dimensional microstructures, based on two-photon polymerization direct laser writing, a fabrication method that allows submicrometric spatial resolution. The structural integrity of the structures was inferred by scanning electron microscopy, while the presence and distribution of ZnO nanowires was investigated by energy dispersive X-ray, Raman spectroscopy, and X-ray diffraction. The optical properties of the produced composite microstructures were verified by imaging the characteristic ZnO emission using a fluorescence microscope. Hence, such approach can be used to develop composite microstructures containing ZnO nanowires aiming at technological applications. © 2013 Wiley Periodicals, Inc. J. Polym. Sci. Part B: Polym. Phys. 2014, 52, 333-337 Zinc oxide (ZnO) has proven to be a promising material for optoelectronic devices operating in the blue to near-UV spectral region. While ZnO/polymer composite films have been readily produced via cast and spin coating, these standard approaches do not allow the fabrication of three-dimensional (3D) microstructures due to the lack of spatial resolution. In this work, 3D microstructures of composites made up of acrylic resin and ZnO nanowires are created by using two-photon polymerization.

Tailoring properties of materials by femtosecond laser processing has been proposed in the last decade as a powerful approach for technological applications, ranging from optics to biology. Although most of the research output in this field is related to femtosecond laser processing of single either organic or inorganic materials, more recently a similar approach has been proposed to develop advanced hybrid nanomaterials. Here, we report results on the use of femtosecond lasers to process hybrid nanomaterials, composed of polymeric and glassy matrices containing metal or semiconductor nanostructures. We present results on the use of femtosecond pulses to induce Cu and Ag nanoparticles in the bulk of borate and borosilicate glasses, which can be applied for a new generation of waveguides. We also report on 3D polymeric structures, fabricated by two-photon polymerization, containing Au and ZnO nanostructures, with intense two-photon fluorescent properties. The approach based on femtosecond laser processing to fabricate hybrid materials containing metal or semiconductor nanostructures is promising to be exploited for optical sensors and photonics devices.

A hybrid assembly was built using ZnO nanowire (NW) arrays and colloidal CdSe quantum dots (QDs) stabilized by 3-mercaptopropionic acid (MPA). The QDs were chemically linked to the nanowires through the bonds formed between the outgoing carboxyl groups of the QD stabilizers and the zinc ions on the nanowire surface. An efficient clustering attachment of the QDs was achieved via partial removal of the stabilizers of the QDs. The photoconductivity of the NW/QD assembly was investigated by selective excitation of the CdSe QDs. Oxygen desorption from the nanowire surface enhances the photoconductivity and a model involving electron transfer between the QDs and the nanowires is proposed to explain the experimental results.

Irradiation of semiconductors with intense femtosecond laser-pulses has recently been demonstrated to provide a versatile means for the fabrication of new materials. Crystalline semiconductors subject to locally intense excitation conditions undergo a transformation: the atomic structure becomes instantaneously disordered and new compounds are “locked in” as the substrate re-crystallizes. Applying this technique to silicon wafers in SF6 ambient, a highly sulfur doped, optically opaque and hundreds of times more light sensitive surface layer has already been demonstrated (black silicon). Additionally, periodic nano- and microstructures appear on the surface of the wafer that lead to a strong scattering of incident light. This versatile technique can be extended to other technologically important materials to modify local material properties and create doping profiles with micrometer resolution as well as to study laser-induced periodic structures.

We report on the photoluminescence properties of ZnO nanowires treated with a mild Ar plasma. The nanowires exhibited stable and strong enhancement of the near-band-edge emission and quenching of the deep level emission. The low temperature PL revealed a strong hydrogen donor-bound-exciton line in the plasma-treated samples indicating unintentional incorporation of hydrogen during the plasma treatment. To confirm the results, hydrogen was implanted into the ZnO nanowires with a low ion energy of 600 eV and different fluences. The observed result can be related to the passivation of deep centers by hydrogen. The absolute photoluminescence intensity measured by an integrating sphere showed stable and strong UV emission from the treated samples even after several weeks.

ZnO nanosheets, nanonails, and well-aligned nanorods were fabricated on Zn foils by a solvothermal approach using ethanol as the solvent. A lower synthesis temperature and a shorter time period favor the formation of nanosheets. By optimizing the synthesis temperature and time period, ZnO nanonails with a hexagonal cap and a long stem could be produced. A higher temperature was not favorable to produce uniform and smooth nanorods. Well-aligned ZnO nanorod arrays were produced with diameters within 100-250 nm and lengths up to approximately 6 microm when NaOH was added to the solvent. By optimizing the reaction parameters, the morphology, size, and orientation of the nanoforms could be tailored. The ZnO nanorods exhibit an excitonic strong UV emission and a defect-related broad green emission at room temperature. The defect-related green emission band decreased with the improvement of the degree of alignment of the nanorods.

Functional ZnO-nanowire/polymer core-shell heterostructures were realized using oxidative chemical vapour deposition (oCVD). This dry and versatile technique allows uniform coating of semiconductor nanowires with polymers and simultaneous doping control of the shell. Here, 100 nm thick, p-doped shells of poly(3,4-ethylenedioxythiophene) (PEDOT) were deposited around n-conductive ZnO nanowires. Energy-dispersive x-ray spectroscopy confirms the incorporation of Br dopants into the PEDOT shell, and the resulting p-conductivity of the polymer shell is demonstrated by electrical measurements on nanowire arrays. Photoluminescence spectroscopy points to reactions of Br with the ZnO surface but proves that the nanowires show only little degradation of their optical properties.

We present fabrication and optical characterization of Si microstructure-ZnO nanowire (NWs) hierarchical structures for light management. Random and periodic hierarchical structures constituting Si micro pillar or micro pyramid arrays with overgrown ZnO NWs have been fabricated. Inexpensive colloidal lithography in combination with dry and wet chemical etching is used to fabricate Si microstructures, and ZnO NWs are grown by hydrothermal synthesis. The periodic Si micro pyramid-ZnO NWs hierarchical structure shows broadband antireflection with average reflectance as low as 2.5% in the 300-1000 nm wavelength range. A tenfold enhancement in Raman intensity is observed in this structure compared to planar Si sample. These hierarchical structures with enriched optical properties and high surface to volume ratio are promising for photovoltaic (PV) and sensor applications.

High material quality InP-based multilayer nanopillar (NP) arrays are fabricated using a combination of self-assembly of silica particles for mask generation and dry etching. In particular, the NP arrays are made from user-defined epitaxial multilayer stacks with specific materials and layer thicknesses. An additional degree of flexibility in the structures is obtained by changing the lateral diameters of the NP multilayer stacks. Pre-defined NP arrays made from InGaAsP/InP and InGaAs/InP NPs are then used to generate substrate-free nanodisks of a chosen material from the stack by selective etching. A soft-stamping method is demonstrated to transfer the generated nanodisks with arbitrary densities onto Si. The transferred nanodisks retain their smooth surface morphologies and their designed geometrical dimensions. Both InP and InGaAsP nanodisks display excellent photoluminescence properties, with line-widths comparable to unprocessed reference epitaxial layers of similar composition. The multilayer NP arrays are potentially attractive for broad-band absorption in third-generation solar cells. The high optical quality, substrate-free InP and InGaAsP nanodisks on Si offer a new path to explore alternative ways to integrate III-V on Si by bonding nanodisks to Si. The method also has the advantage of re-usable III-V substrates for subsequent layer growth.

Surface structuring with ultrashort laser pulses is of high interest as a scalable doping technique as well as for surface nanostructuring applications. By depositing a layer of antimony before the irradiation of ZnO, we were able to incorporate a large quantity of Sb atoms into the single crystalline region of the laser modified surface for potential p-type doping. We have studied the incorporation of antimony and the material properties of laser-induced periodic surface structures (LIPSS) on c-plane ZnO upon femtosecond laser processing at two different peak fluences. We observe high spatial frequency LIPSS with structure periods from 200–370 nm and low spatial frequency LIPSS with periods of 600–700 nm. At a fluence of 0.8 J/cm2, close the ablation threshold of ZnO, the LIPSS are single crystalline except for a few nanometers of amorphous material. At a peak laser fluence of 3.1 J/cm2, they consist of polycrystalline and single crystalline ZnO areas. However, the polycrystalline part dominates with a thickness of about 500 nm.

We investigated the photoluminescence properties of ZnO nanowires coated with Au, Ag, and Pt nanoparticles deposited by dc sputtering. A strong enhancement of the near-band-edge emission was observed in all metal-coated samples but also if the samples were treated with Ar plasma without any nanoparticle deposition. High-resolution photoluminescence spectroscopy revealed hydrogen-donor-bound-exciton emission in all samples indicating unintentional hydrogen incorporation. A shorter decay time of the near-band-edge emission was observed in all cases. The results indicate that unintentional hydrogen incorporation plays a dominant role when metal deposition is performed by sputtering.

The influence of the Zn(2+) concentration and temperature on the electrochemical reduction of O(2) in a solution of zinc bis(trifluoromethanesulfonyl)imide (Zn(TFSI)(2)) salt in 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR(14)TFSI) ionic liquid is presented. ZnO nanocrystalline films were then electrodeposited, under enhanced O(2) reduction, at temperatures in the 75-150 °C range. Their morphology, chemical composition, structural and optical properties were analyzed. In contrast to the polar-oriented ZnO usually obtained from aqueous and conventional solvent based electrolytes, nanocrystalline films oriented along non-polar directions, (11 ̅10) and (11 ̅20), were obtained from this ionic liquid electrolyte. A significant content of carbon was detected in the films, pointing to the active participation and crucial effect of pyrrolidinium cation (and/or byproducts) during the electrodeposition. The films showed semiconducting behavior with an optical gap between 3.43 and 3.53 eV as measured by optical transmittance. Their room temperature photoluminescence spectra exhibited two different bands centered at ∼3.4 and ∼2.2 eV. The intensity ratio between both bands was found to depend on the deposition temperature. This work demonstrates the great potential of ionic liquids based electrolytes for the electrodeposition of ZnO nanocrystalline thin films with innovative microstructural and optoelectronic properties.