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1.  Gas Sensors Based on One Dimensional Nanostructured Metal-Oxides: A Review 
Sensors (Basel, Switzerland)  2012;12(6):7207-7258.
Recently one dimensional (1-D) nanostructured metal-oxides have attracted much attention because of their potential applications in gas sensors. 1-D nanostructured metal-oxides provide high surface to volume ratio, while maintaining good chemical and thermal stabilities with minimal power consumption and low weight. In recent years, various processing routes have been developed for the synthesis of 1-D nanostructured metal-oxides such as hydrothermal, ultrasonic irradiation, electrospinning, anodization, sol-gel, molten-salt, carbothermal reduction, solid-state chemical reaction, thermal evaporation, vapor-phase transport, aerosol, RF sputtering, molecular beam epitaxy, chemical vapor deposition, gas-phase assisted nanocarving, UV lithography and dry plasma etching. A variety of sensor fabrication processing routes have also been developed. Depending on the materials, morphology and fabrication process the performance of the sensor towards a specific gas shows a varying degree of success. This article reviews and evaluates the performance of 1-D nanostructured metal-oxide gas sensors based on ZnO, SnO2, TiO2, In2O3, WOx, AgVO3, CdO, MoO3, CuO, TeO2 and Fe2O3. Advantages and disadvantages of each sensor are summarized, along with the associated sensing mechanism. Finally, the article concludes with some future directions of research.
doi:10.3390/s120607207
PMCID: PMC3435973  PMID: 22969344
gas sensor; one dimensional nanostructures; metal-oxides
2.  Prospects of Nanotechnology in Clinical Immunodiagnostics 
Sensors (Basel, Switzerland)  2010;10(7):6535-6581.
Nanostructured materials are promising compounds that offer new opportunities as sensing platforms for the detection of biomolecules. Having micrometer-scale length and nanometer-scale diameters, nanomaterials can be manipulated with current nanofabrication methods, as well as self-assembly techniques, to fabricate nanoscale bio-sensing devices. Nanostructured materials possess extraordinary physical, mechanical, electrical, thermal and multifunctional properties. Such unique properties advocate their use as biomimetic membranes to immobilize and modify biomolecules on the surface of nanoparticles. Alignment, uniform dispersion, selective growth and diameter control are general parameters which play critical roles in the successful integration of nanostructures for the fabrication of bioelectronic sensing devices. In this review, we focus on different types and aspects of nanomaterials, including their synthesis, properties, conjugation with biomolecules and their application in the construction of immunosensing devices. Some key results from each cited article are summarized by relating the concept and mechanism behind each sensor, experimental conditions and the behavior of the sensor under different conditions, etc. The variety of nanomaterial-based bioelectronic devices exhibiting novel functions proves the unique properties of nanomaterials in such sensing devices, which will surely continue to expand in the future. Such nanomaterial based devices are expected to have a major impact in clinical immunodiagnostics, environmental monitoring, security surveillance and for ensuring food safety.
doi:10.3390/s100706535
PMCID: PMC3231125  PMID: 22163566
nanotechnology; antibody; antigen; nanomaterials; immune-biosensors
3.  Hydrogen Gas Sensors Based on Semiconductor Oxide Nanostructures 
Sensors (Basel, Switzerland)  2012;12(5):5517-5550.
Recently, the hydrogen gas sensing properties of semiconductor oxide (SMO) nanostructures have been widely investigated. In this article, we provide a comprehensive review of the research progress in the last five years concerning hydrogen gas sensors based on SMO thin film and one-dimensional (1D) nanostructures. The hydrogen sensing mechanism of SMO nanostructures and some critical issues are discussed. Doping, noble metal-decoration, heterojunctions and size reduction have been investigated and proved to be effective methods for improving the sensing performance of SMO thin films and 1D nanostructures. The effect on the hydrogen response of SMO thin films and 1D nanostructures of grain boundary and crystal orientation, as well as the sensor architecture, including electrode size and nanojunctions have also been studied. Finally, we also discuss some challenges for the future applications of SMO nanostructured hydrogen sensors.
doi:10.3390/s120505517
PMCID: PMC3386698  PMID: 22778599
hydrogen gas sensor; semiconductor oxides; nanostructure; thin films; one-dimensional nanostructures
4.  Scalable Manufacturing of Plasmonic Nanodisk Dimers and Cusp Nanostructures using Salting-out Quenching Method and Colloidal Lithography 
ACS nano  2011;5(7):5838-5847.
Localization of large electric fields in plasmonic nanostructures enables various processes such as single molecule detection, higher harmonic light generation, and control of molecular fluorescence and absorption. High-throughput, simple nanofabrication techniques are essential for implementing plasmonic nanostructures with large electric fields for practical applications. In this article we demonstrate a scalable, rapid, and inexpensive fabrication method based on the salting-out quenching technique and colloidal lithography for the fabrication of two types of nanostructures with large electric field: nanodisk dimers and cusp nanostructures. Our technique relies on fabricating polystyrene doublets from single beads by controlled aggregation and later using them as soft masks to fabricate metal nanodisk dimers and nanocusp structures. Both of these structures have a well-defined geometry for the localization of large electric fields comparable to structures fabricated by conventional nanofabrication techniques. We also show that various parameters in the fabrication process can be adjusted to tune the geometry of the final structures and control their plasmonic properties. With advantages in throughput, cost, and geometric tunability, our fabrication method can be valuable in many applications that require plasmonic nanostructures with large electric fields.
doi:10.1021/nn201595x
PMCID: PMC3989542  PMID: 21692473
Nanoparticle Dimers; Nanocusp Structures; Colloidal Lithography; Large Electric Field; Surface Enhanced Raman Scattering (SERS); Salting-out Quenching; Colloidal Doublets
5.  Metal Oxide Nanosensors Using Polymeric Membranes, Enzymes and Antibody Receptors as Ion and Molecular Recognition Elements 
Sensors (Basel, Switzerland)  2014;14(5):8605-8632.
The concept of recognition and biofunctionality has attracted increasing interest in the fields of chemistry and material sciences. Advances in the field of nanotechnology for the synthesis of desired metal oxide nanostructures have provided a solid platform for the integration of nanoelectronic devices. These nanoelectronics-based devices have the ability to recognize molecular species of living organisms, and they have created the possibility for advanced chemical sensing functionalities with low limits of detection in the nanomolar range. In this review, various metal oxides, such as ZnO-, CuO-, and NiO-based nanosensors, are described using different methods (receptors) of functionalization for molecular and ion recognition. These functionalized metal oxide surfaces with a specific receptor involve either a complex formation between the receptor and the analyte or an electrostatic interaction during the chemical sensing of analytes. Metal oxide nanostructures are considered revolutionary nanomaterials that have a specific surface for the immobilization of biomolecules with much needed orientation, good conformation and enhanced biological activity which further improve the sensing properties of nanosensors. Metal oxide nanostructures are associated with certain unique optical, electrical and molecular characteristics in addition to unique functionalities and surface charge features which shows attractive platforms for interfacing biorecognition elements with effective transducing properties for signal amplification. There is a great opportunity in the near future for metal oxide nanostructure-based miniaturization and the development of engineering sensor devices.
doi:10.3390/s140508605
PMCID: PMC4063009  PMID: 24841244
ZnO nanostructures; CuO nanostructures; NiO nanostructures; potentiometric nanosensors; biosensors; chemical sensors
6.  Metal Oxide Nanostructures and Their Gas Sensing Properties: A Review 
Sensors (Basel, Switzerland)  2012;12(3):2610-2631.
Metal oxide gas sensors are predominant solid-state gas detecting devices for domestic, commercial and industrial applications, which have many advantages such as low cost, easy production, and compact size. However, the performance of such sensors is significantly influenced by the morphology and structure of sensing materials, resulting in a great obstacle for gas sensors based on bulk materials or dense films to achieve highly-sensitive properties. Lots of metal oxide nanostructures have been developed to improve the gas sensing properties such as sensitivity, selectivity, response speed, and so on. Here, we provide a brief overview of metal oxide nanostructures and their gas sensing properties from the aspects of particle size, morphology and doping. When the particle size of metal oxide is close to or less than double thickness of the space-charge layer, the sensitivity of the sensor will increase remarkably, which would be called “small size effect”, yet small size of metal oxide nanoparticles will be compactly sintered together during the film coating process which is disadvantage for gas diffusion in them. In view of those reasons, nanostructures with many kinds of shapes such as porous nanotubes, porous nanospheres and so on have been investigated, that not only possessed large surface area and relatively mass reactive sites, but also formed relatively loose film structures which is an advantage for gas diffusion. Besides, doping is also an effective method to decrease particle size and improve gas sensing properties. Therefore, the gas sensing properties of metal oxide nanostructures assembled by nanoparticles are reviewed in this article. The effect of doping is also summarized and finally the perspectives of metal oxide gas sensor are given.
doi:10.3390/s120302610
PMCID: PMC3376589  PMID: 22736968
metal oxide; gas sensing; nanostructure; size effect; doping
7.  Nanostructured Gas Sensors for Health Care: An Overview 
Nanostructured platforms have been utilized for fabrication of small, sensitive and reliable gas sensing devices owing to high functionality, enhanced charge transport and electro-catalytic property. As a result of globalization, rapid, sensitive and selective detection of gases in environment is essential for health care and security. Nonmaterial such as metal, metal oxides, organic polymers, and organic-inorganic hybrid nanocomposites exhibit interesting optical, electrical, magnetic and molecular properties, and hence are found potential gas sensing materials. Morphological, electrical, and optical properties of such nanostructures can be tailored via controlling the precursor concentration and synthesis conditions resulting to achieve desired sensing. This review presents applications of nano-enabling gas sensors to detect gases for environment monitoring. The recent update, challenges, and future vision for commercial applications of such sensor are also described here.
PMCID: PMC4610411  PMID: 26491544
Nanotechnology; Conducting polymers; Metal oxides; Organic-Inorganic hybrid nanocomposites; Gas sensors
8.  Gas Sensors Based on Semiconducting Nanowire Field-Effect Transistors 
Sensors (Basel, Switzerland)  2014;14(9):17406-17429.
One-dimensional semiconductor nanostructures are unique sensing materials for the fabrication of gas sensors. In this article, gas sensors based on semiconducting nanowire field-effect transistors (FETs) are comprehensively reviewed. Individual nanowires or nanowire network films are usually used as the active detecting channels. In these sensors, a third electrode, which serves as the gate, is used to tune the carrier concentration of the nanowires to realize better sensing performance, including sensitivity, selectivity and response time, etc. The FET parameters can be modulated by the presence of the target gases and their change relate closely to the type and concentration of the gas molecules. In addition, extra controls such as metal decoration, local heating and light irradiation can be combined with the gate electrode to tune the nanowire channel and realize more effective gas sensing. With the help of micro-fabrication techniques, these sensors can be integrated into smart systems. Finally, some challenges for the future investigation and application of nanowire field-effect gas sensors are discussed.
doi:10.3390/s140917406
PMCID: PMC4208231  PMID: 25232915
gas sensors; semiconducting nanowires; field effect transistors
9.  Gas Sensors Based on Semiconducting Metal Oxide One-Dimensional Nanostructures 
Sensors (Basel, Switzerland)  2009;9(12):9903-9924.
This article provides a comprehensive review of recent (2008 and 2009) progress in gas sensors based on semiconducting metal oxide one-dimensional (1D) nanostructures. During last few years, gas sensors based on semiconducting oxide 1D nanostructures have been widely investigated. Additionally, modified or doped oxide nanowires/nanobelts have also been synthesized and used for gas sensor applications. Moreover, novel device structures such as electronic noses and low power consumption self-heated gas sensors have been invented and their gas sensing performance has also been evaluated. Finally, we also point out some challenges for future investigation and practical application.
doi:10.3390/s91209903
PMCID: PMC3267202  PMID: 22303154
gas sensors; semiconducting oxides; one-dimensional nanostructures
10.  A Comprehensive Review of One-Dimensional Metal-Oxide Nanostructure Photodetectors 
Sensors (Basel, Switzerland)  2009;9(8):6504-6529.
One-dimensional (1D) metal-oxide nanostructures are ideal systems for exploring a large number of novel phenomena at the nanoscale and investigating size and dimensionality dependence of nanostructure properties for potential applications. The construction and integration of photodetectors or optical switches based on such nanostructures with tailored geometries have rapidly advanced in recent years. Active 1D nanostructure photodetector elements can be configured either as resistors whose conductions are altered by a charge-transfer process or as field-effect transistors (FET) whose properties can be controlled by applying appropriate potentials onto the gates. Functionalizing the structure surfaces offers another avenue for expanding the sensor capabilities. This article provides a comprehensive review on the state-of-the-art research activities in the photodetector field. It mainly focuses on the metal oxide 1D nanostructures such as ZnO, SnO2, Cu2O, Ga2O3, Fe2O3, In2O3, CdO, CeO2, and their photoresponses. The review begins with a survey of quasi 1D metal-oxide semiconductor nanostructures and the photodetector principle, then shows the recent progresses on several kinds of important metal-oxide nanostructures and their photoresponses and briefly presents some additional prospective metal-oxide 1D nanomaterials. Finally, the review is concluded with some perspectives and outlook on the future developments in this area.
doi:10.3390/s90806504
PMCID: PMC3312456  PMID: 22454597
metal oxide semiconductor; one-dimensional nanostructures; sensor; photodetector; transistor
11.  Uniform metal nanostructures with long-range order via three-step hierarchical self-assembly 
Science Advances  2015;1(10):e1500751.
Bottom-up routine enables precise metal nanopatterning on large areas, overcoming the limits of top-down fabrication methods.
Large-scale nanopatterning is a major issue in nanoscience and nanotechnology, but conventional top-down approaches are challenging because of instrumentation and process complexity while often lacking the desired spatial resolution. We present a hierarchical bottom-up nanopatterning routine using exclusively self-assembly processes: By combining crystal surface reconstruction, microphase separation of copolymers, and selective metal diffusion, we produce monodisperse metal nanostructures in highly regular arrays covering areas of square centimeters. In situ grazing incidence small-angle x-ray scattering during Fe nanostructure formation evidences an outstanding structural order in the self-assembling system and hints at the possibility of sculpting nanostructures using external process parameters. Thus, we demonstrate that bottom-up nanopatterning is a competitive alternative to top-down routines, achieving comparable pattern regularity, feature size, and patterned areas with considerably reduced effort. Intriguing assets of the proposed fabrication approach include the option for in situ investigations during pattern formation, the possibility of customizing the nanostructure morphology, the capacity to pattern arbitrarily large areas with ultrahigh structure densities unachievable by top-down approaches, and the potential to address the nanostructures individually. Numerous applications of self-assembled nanostructure patterns can be envisioned, for example, in high-density magnetic data storage, in functional nanostructured materials for photonics or catalysis, or in surface plasmon resonance–based sensing.
doi:10.1126/sciadv.1500751
PMCID: PMC4640591  PMID: 26601139
hierarchical self-assembly; bottom-up nanopatterning; polymer-metal nanocomposite materials; magnetic nanostructures; diblock copolymer thin films; GISAXS at synchrotron radiation source
12.  The design, fabrication, and photocatalytic utility of nanostructured semiconductors: focus on TiO2-based nanostructures 
Recent advances in basic fabrication techniques of TiO2-based nanomaterials such as nanoparticles, nanowires, nanoplatelets, and both physical- and solution-based techniques have been adopted by various research groups around the world. Our research focus has been mainly on various deposition parameters used for fabricating nanostructured materials, including TiO2-organic/inorganic nanocomposite materials. Technically, TiO2 shows relatively high reactivity under ultraviolet light, the energy of which exceeds the band gap of TiO2. The development of photocatalysts exhibiting high reactivity under visible light allows the main part of the solar spectrum to be used. Visible light-activated TiO2 could be prepared by doping or sensitizing. As far as doping of TiO2 is concerned, in obtaining tailored material with improved properties, metal and nonmetal doping has been performed in the context of improved photoactivity. Nonmetal doping seems to be more promising than metal doping. TiO2 represents an effective photocatalyst for water and air purification and for self-cleaning surfaces. Additionally, it can be used as an antibacterial agent because of its strong oxidation activity and superhydrophilicity. Therefore, applications of TiO2 in terms of photocatalytic activities are discussed here. The basic mechanisms of the photoactivities of TiO2 and nanostructures are considered alongside band structure engineering and surface modification in nanostructured TiO2 in the context of doping. The article reviews the basic structural, optical, and electrical properties of TiO2, followed by detailed fabrication techniques of 0-, 1-, and quasi-2-dimensional TiO2 nanomaterials. Applications and future directions of nanostructured TiO2 are considered in the context of various photoinduced phenomena such as hydrogen production, electricity generation via dye-sensitized solar cells, photokilling and self-cleaning effect, photo-oxidation of organic pollutant, wastewater management, and organic synthesis.
doi:10.2147/NSA.S9040
PMCID: PMC3781710  PMID: 24198485
TiO2 nanostructure; fabrication techniques; doping in TiO2; TiO2-assisted photoactivity; solar hydrogen; TiO2-based dye-sensitized solar cells; TiO2 self-cleaning; organic synthesis
13.  The Kirkendall effect and nanoscience: hollow nanospheres and nanotubes 
Summary
Hollow nanostructures are ranked among the top materials for applications in various modern technological areas including energy storage devices, catalyst, optics and sensors. The last years have witnessed increasing interest in the Kirkendall effect as a versatile route to fabricate hollow nanostructures with different shapes, compositions and functionalities. Although the conversion chemistry of nanostructures from solid to hollow has reached a very advanced maturity, there is still much to be discovered and learned on this effect. Here, the recent progress on the use of the Kirkendall effect to synthesize hollow nanospheres and nanotubes is reviewed with a special emphasis on the fundamental mechanisms occurring during such a conversion process. The discussion includes the oxidation of metal nanostructures (i.e., nanospheres and nanowires), which is an important process involving the Kirkendall effect. For nanospheres, the symmetrical and the asymmetrical mechanisms are both reviewed and compared on the basis of recent reports in the literature. For nanotubes, in addition to a summary of the conversion processes, the unusual effects observed in some particular cases (e.g., formation of segmented or bamboo-like nanotubes) are summarized and discussed. Finally, we conclude with a summary, where the prospective future direction of this research field is discussed.
doi:10.3762/bjnano.6.139
PMCID: PMC4505174  PMID: 26199838
hollow nanospheres; Kirkendall effect; metals; nanotubes; oxides
14.  Nanostructures: a platform for brain repair and augmentation 
Nanoscale structures have been at the core of research efforts dealing with integration of nanotechnology into novel electronic devices for the last decade. Because the size of nanomaterials is of the same order of magnitude as biomolecules, these materials are valuable tools for nanoscale manipulation in a broad range of neurobiological systems. For instance, the unique electrical and optical properties of nanowires, nanotubes, and nanocables with vertical orientation, assembled in nanoscale arrays, have been used in many device applications such as sensors that hold the potential to augment brain functions. However, the challenge in creating nanowires/nanotubes or nanocables array-based sensors lies in making individual electrical connections fitting both the features of the brain and of the nanostructures. This review discusses two of the most important applications of nanostructures in neuroscience. First, the current approaches to create nanowires and nanocable structures are reviewed to critically evaluate their potential for developing unique nanostructure based sensors to improve recording and device performance to reduce noise and the detrimental effect of the interface on the tissue. Second, the implementation of nanomaterials in neurobiological and medical applications will be considered from the brain augmentation perspective. Novel applications for diagnosis and treatment of brain diseases such as multiple sclerosis, meningitis, stroke, epilepsy, Alzheimer's disease, schizophrenia, and autism will be considered. Because the blood brain barrier (BBB) has a defensive mechanism in preventing nanomaterials arrival to the brain, various strategies to help them to pass through the BBB will be discussed. Finally, the implementation of nanomaterials in neurobiological applications is addressed from the brain repair/augmentation perspective. These nanostructures at the interface between nanotechnology and neuroscience will play a pivotal role not only in addressing the multitude of brain disorders but also to repair or augment brain functions.
doi:10.3389/fnsys.2014.00091
PMCID: PMC4064704  PMID: 24999319
nanotechnology; brain repair and augmentation; brain activity mapping; blood brain barrier; carbon nanotube; multi-electrode array; nano-imprint lithography; inter-laminar microcircuit
15.  Morphological and chemical stability of silicon nanostructures and their molecular overlayers under physiological conditions: towards long-term implantable nanoelectronic biosensors 
Background
The detection of biological and chemical species is of key importance to numerous areas of medical and life sciences. Therefore, a great interest exists in developing new, rapid, miniature, biocompatible and highly sensitive sensors, capable to operate under physiological conditions and displaying long-term stabilities (e.g. in-body implantable sensors). Silicon nanostructures, nanowires and nanotubes, have been extensively explored as building blocks for the creation of improved electrical biosensing devices, by virtue of their remarkably high surface-to-volume ratios, and have shown exceptional sensitivity for the real time label-free detection of molecular species adsorbed on their surfaces, down to the sensitivity of single molecules.
Yet, till this date, almost no rigorous studies have been performed on the temporal morphological stability of these nanostructures, and their resulting electrical devices, under physiological conditions (e.g. serum, blood), as well as on the chemical stability of the molecular recognition over-layers covering these structures.
Results
Here, we present systematic time-resolved results on the morphological stability of bare Si nanowire building blocks, as well on the chemical stability of siloxane-based molecular over-layers, under physiological conditions. Furthermore, in order to overcome the observed short-term morpho-chemical instabilities, we present on the chemical passivation of the Si nanostructures by thin metal oxide nanoshells, in the range of 3–10 nm. The thickness of the metal oxide layer influences on the resulting electrical sensitivity of the fabricated FETs (field effect transistors), with an optimum thickness of 3–4 nm.
Conclusions
The core-shell structures display remarkable long-term morphological stability, preventing both, the chemical hydrolytic dissolution of the silicon under-structure and the concomitant loss of the siloxane-based chemical over-layers, for periods of at least several months. Electrical devices constructed from these nanostructures display excellent electrical characteristics and detection sensitivities, with exceptionally high morphological and functional stabilities. These results pave the road for the creation of long-term implantable biosensing devices in general, and nanodevices in particular.
doi:10.1186/1477-3155-12-7
PMCID: PMC3975481  PMID: 24606762
Nanowire; Field effect transistors; Chemical stability; Silicon; Dissolution; Biosensors
16.  Boron Nitride Nanotubes for Spintronics 
Sensors (Basel, Switzerland)  2014;14(9):17655-17685.
With the end of Moore's law in sight, researchers are in search of an alternative approach to manipulate information. Spintronics or spin-based electronics, which uses the spin state of electrons to store, process and communicate information, offers exciting opportunities to sustain the current growth in the information industry. For example, the discovery of the giant magneto resistance (GMR) effect, which provides the foundation behind modern high density data storage devices, is an important success story of spintronics; GMR-based sensors have wide applications, ranging from automotive industry to biology. In recent years, with the tremendous progress in nanotechnology, spintronics has crossed the boundary of conventional, all metallic, solid state multi-layered structures to reach a new frontier, where nanostructures provide a pathway for the spin-carriers. Different materials such as organic and inorganic nanostructures are explored for possible applications in spintronics. In this short review, we focus on the boron nitride nanotube (BNNT), which has recently been explored for possible applications in spintronics. Unlike many organic materials, BNNTs offer higher thermal stability and higher resistance to oxidation. It has been reported that the metal-free fluorinated BNNT exhibits long range ferromagnetic spin ordering, which is stable at a temperature much higher than room temperature. Due to their large band gap, BNNTs are also explored as a tunnel magneto resistance device. In addition, the F-BNNT has recently been predicted as an ideal spin-filter. The purpose of this review is to highlight these recent progresses so that a concerted effort by both experimentalists and theorists can be carried out in the future to realize the true potential of BNNT-based spintronics.
doi:10.3390/s140917655
PMCID: PMC4208243  PMID: 25248070
electronic structure; spintronics; spin-valve; ferromagnetic spin ordering; transverse electric field; radial deformation; functionalization; magnetism; tunneling magneto-resistance; spin filtering
17.  Low-Dimensional Palladium Nanostructures for Fast and Reliable Hydrogen Gas Detection 
Sensors (Basel, Switzerland)  2011;11(1):825-851.
Palladium (Pd) has received attention as an ideal hydrogen sensor material due to its properties such as high sensitivity and selectivity to hydrogen gas, fast response, and operability at room temperature. Interestingly, various Pd nanostructures that have been realized by recent developments in nanotechnologies are known to show better performance than bulk Pd. This review highlights the characteristic properties, issues, and their possible solutions of hydrogen sensors based on the low-dimensional Pd nanostructures with more emphasis on Pd thin films and Pd nanowires. The finite size effects, relative strengths and weaknesses of the respective Pd nanostructures are discussed in terms of performance, manufacturability, and practical applicability.
doi:10.3390/s110100825
PMCID: PMC3274109  PMID: 22346605
Pd nanostructures; hydrogen sensors
18.  Near-field effects and energy transfer in hybrid metal-oxide nanostructures 
Summary
One of the big challenges of the 21st century is the utilization of nanotechnology for energy technology. Nanoscale structures may provide novel functionality, which has been demonstrated most convincingly by successful applications such as dye-sensitized solar cells introduced by M. Grätzel. Applications in energy technology are based on the transfer and conversion of energy. Following the example of photosynthesis, this requires a combination of light harvesting, transfer of energy to a reaction center, and conversion to other forms of energy by charge separation and transfer. This may be achieved by utilizing hybrid nanostructures, which combine metallic and nonmetallic components. Metallic nanostructures can interact strongly with light. Plasmonic excitations of such structures can cause local enhancement of the electrical field, which has been utilized in spectroscopy for many years. On the other hand, the excited states in metallic structures decay over very short lifetimes. Longer lifetimes of excited states occur in nonmetallic nanostructures, which makes them attractive for further energy transfer before recombination or relaxation sets in. Therefore, the combination of metallic nanostructures with nonmetallic materials is of great interest. We report investigations of hybrid nanostructured model systems that consist of a combination of metallic nanoantennas (fabricated by nanosphere lithography, NSL) and oxide nanoparticles. The oxide particles were doped with rare-earth (RE) ions, which show a large shift between absorption and emission wavelengths, allowing us to investigate the energy-transfer processes in detail. The main focus is on TiO2 nanoparticles doped with Eu3+, since the material is interesting for applications such as the generation of hydrogen by photocatalytic splitting of water molecules. We use high-resolution techniques such as confocal fluorescence microscopy for the investigation of energy-transfer processes. The experiments are supported by simulations of the electromagnetic field enhancement in the vicinity of well-defined nanoantennas. The results show that the presence of the nanoparticle layer can modify the field enhancement significantly. In addition, we find that the fluorescent intensities observed in the experiments are affected by agglomeration of the nanoparticles. In order to further elucidate the possible influence of agglomeration and quenching effects in the vicinity of the nanoantennas, we have used a commercial organic pigment containing Eu, which exhibits an extremely narrow particle size distribution and no significant agglomeration. We demonstrate that quenching of the Eu fluorescence can be suppressed by covering the nanoantennas with a 10 nm thick SiOx layer.
doi:10.3762/bjnano.4.34
PMCID: PMC3678447  PMID: 23766954
confocal microscopy; energy transfer; field enhancement; light harvesting; luminescence; nano-antennas; nanosphere lithography; nanostructures; plasmonics; simulation; TiO2 nanoparticles
19.  Protein Biosensors Based on Polymer Nanowires, Carbon Nanotubes and Zinc Oxide Nanorods 
Sensors (Basel, Switzerland)  2011;11(5):5087-5111.
The development of biosensors using electrochemical methods is a promising application in the field of biotechnology. High sensitivity sensors for the bio-detection of proteins have been developed using several kinds of nanomaterials. The performance of the sensors depends on the type of nanostructures with which the biomaterials interact. One dimensional (1-D) structures such as nanowires, nanotubes and nanorods are proven to have high potential for bio-applications. In this paper we review these three different kinds of nanostructures that have attracted much attention at recent times with their great performance as biosensors. Materials such as polymers, carbon and zinc oxide have been widely used for the fabrication of nanostructures because of their enhanced performance in terms of sensitivity, biocompatibility, and ease of preparation. Thus we consider polymer nanowires, carbon nanotubes and zinc oxide nanorods for discussion in this paper. We consider three stages in the development of biosensors: (a) fabrication of biomaterials into nanostructures, (b) alignment of the nanostructures and (c) immobilization of proteins. Two different methods by which the biosensors can be developed at each stage for all the three nanostructures are examined. Finally, we conclude by mentioning some of the major challenges faced by many researchers who seek to fabricate biosensors for real time applications.
doi:10.3390/s110505087
PMCID: PMC3231366  PMID: 22163892
biosensor; nanostructures; electrochemical; immobilization
20.  Design Concepts, Fabrication and Advanced Characterization Methods of Innovative Piezoelectric Sensors Based on ZnO Nanowires 
Sensors (Basel, Switzerland)  2014;14(12):23539-23562.
Micro- and nano-scale materials and systems based on zinc oxide are expected to explode in their applications in the electronics and photonics, including nano-arrays of addressable optoelectronic devices and sensors, due to their outstanding properties, including semiconductivity and the presence of a direct bandgap, piezoelectricity, pyroelectricity and biocompatibility. Most applications are based on the cooperative and average response of a large number of ZnO micro/nanostructures. However, in order to assess the quality of the materials and their performance, it is fundamental to characterize and then accurately model the specific electrical and piezoelectric properties of single ZnO structures. In this paper, we report on focused ion beam machined high aspect ratio nanowires and their mechanical and electrical (by means of conductive atomic force microscopy) characterization. Then, we investigate the suitability of new power-law design concepts to accurately model the relevant electrical and mechanical size-effects, whose existence has been emphasized in recent reviews.
doi:10.3390/s141223539
PMCID: PMC4299076  PMID: 25494351
zinc oxide; nanowire; atomic force microscopy; FIB machining; conductive AFM; power-law design; FEM analysis
21.  Aqueous multiphoton lithography with multifunctional silk-centred bio-resists 
Nature Communications  2015;6:8612.
Silk and silk fibroin, the biomaterial from nature, nowadays are being widely utilized in many cutting-edge micro/nanodevices/systems via advanced micro/nanofabrication techniques. Herein, for the first time to our knowledge, we report aqueous multiphoton lithography of diversiform-regenerated-silk-fibroin-centric inks using noncontact and maskless femtosecond laser direct writing (FsLDW). Initially, silk fibroin was FsLDW-crosslinked into arbitrary two/three-dimensional micro/nanostructures with good elastic properties merely using proper photosensitizers. More interestingly, silk/metal composite micro/nanodevices with multidimension-controllable metal content can be FsLDW-customized through laser-induced simultaneous fibroin oxidation/crosslinking and metal photoreduction using the simplest silk/Ag+ or silk/[AuCl4]− aqueous resists. Noticeably, during FsLDW, fibroin functions as biological reductant and matrix, while metal ions act as the oxidant. A FsLDW-fabricated prototyping silk/Ag microelectrode exhibited 104-Ω−1 m−1-scale adjustable electric conductivity. This work not only provides a powerful development to silk micro/nanoprocessing techniques but also creates a novel way to fabricate multifunctional metal/biomacromolecule complex micro/nanodevices for applications such as micro/nanoscale mechanical and electrical bioengineering and biosystems.
Scientists are increasingly realising the potential for natural materials in micro- and nanofabrication. Here, the authors employ silk-based resists for aqueous multiphoton lithography towards generating intricate structures by femtosecond direct writing.
doi:10.1038/ncomms9612
PMCID: PMC4634322  PMID: 26472600
22.  Low Temperature Sensing Properties of a Nano Hybrid Material Based on ZnO Nanotetrapods and Titanyl Phthalocyanine 
Sensors (Basel, Switzerland)  2013;13(3):3445-3453.
ZnO nanotetrapods have recently been exploited for the realization of high-sensitivity gas sensors, but they are affected by the typical drawbacks of metal-oxides, i.e., poor selectivity and a relatively high working temperature. On the other hand, it has been also demonstrated that the combined use of nanostructured metal oxides and organic molecules can improve the gas sensing performance sensitivity or selectivity, even at lower temperatures. A gas sensor device, based on films of interconnected ZnO nanotetrapods properly functionalized by titanyl phthalocyanine (TiOPc), has been realized in order to combine the high surface to volume ratio and structural stability of the crystalline ZnO nanostructures with the enhanced sensitivity of the semiconducting TiOPc molecule, especially at low temperature. The electronic properties of the resulting nanohybrid material are different from those of each single component. The response of the hybrid nanostructure towards different gases has been compared with that of ZnO nanotetrapod without functionalization in order to highlight the peculiar properties of the hybrid interaction(s). The dynamic response in time has been studied for different gases and temperatures; in particular, an increase in the response to NO2 has been observed, even at room temperature. The formation of localized p-n heterojunctions and the possibility of exchanging charge carriers at the hybrid interface is shown to be crucial for the sensing mechanism.
doi:10.3390/s130303445
PMCID: PMC3658755  PMID: 23486215
gas sensor; ZnO nanostructures; phthalocyanine; NO2; room temperature
23.  A New Strategy of Lithography Based on Phase Separation of Polymer Blends 
Scientific Reports  2015;5:15947.
Herein, we propose a new strategy of maskless lithographic approach to fabricate micro/nano-porous structures by phase separation of polystyrene (PS)/Polyethylene glycol (PEG) immiscible polymer blend. Its simple process only involves a spin coating of polymer blend followed by a development with deionized water rinse to remove PEG moiety, which provides an extremely facile, low-cost, easily accessible nanofabrication method to obtain the porous structures with wafer-scale. By controlling the weight ratio of PS/PEG polymer blend, its concentration and the spin-coating speed, the structural parameters of the porous nanostructure could be effectively tuned. These micro/nano porous structures could be converted into versatile functional nanostructures in combination with follow-up conventional chemical and physical nanofabrication techniques. As demonstrations of perceived potential applications using our developed phase separation lithography, we fabricate wafer-scale pure dielectric (silicon)-based two-dimensional nanostructures with high broadband absorption on silicon wafers due to their great light trapping ability, which could be expected for promising applications in the fields of photovoltaic devices and thermal emitters with very good performances, and Ag nanodot arrays which possess a surface enhanced Raman scattering (SERS) enhancement factor up to 1.64 × 108 with high uniformity across over an entire wafer.
doi:10.1038/srep15947
PMCID: PMC4626759  PMID: 26515790
24.  Emerging use of nanostructure films containing capped gold nanoparticles in biosensors 
The localized surface plasmon resonance (LSPR) property of gold nanoparticles (GNP) has been exploited in a variety of optical sensor configurations including solution-based bioassays, paper-based colorimetric detection, surface-confined nanoparticle film/array-based sensing, etc. Amongst these, gold nanostructured films are of great interest because of their high stability, good reproducibility, robustness, and cost-effectiveness. The inherent optical characteristics of GNP, are attributed to parameters like size and shape (eg, nanospheres, nanorods, nanostars), eg, LSPR spectral location sensitivity to the local environment, composition (eg, gold–silver or silica–gold nanoshells), sensing volume, mesospacing, and multiplexing. These properties allow sensor tunability, enabling enhanced sensitivity and better performance of these biosensors. Ultrasensitive biosensor designs were realized using gold nanostructured films fabricated by bottom-up as well as top-down approaches. In this review, we describe the past, present, and future trends in the development of GNP-LSPR-based sensors, concentrating on both design (fabrication) and application. In the process, we have discussed various combinations of GNP size and shape, substrate, and application domains.
doi:10.2147/NSA.S8981
PMCID: PMC3781700  PMID: 24198481
localized surface plasmon resonance; gold nanoparticles; label-free optical biosensor
25.  Au nanostructure arrays for plasmonic applications: annealed island films versus nanoimprint lithography 
This paper attempts to compare the main features of random and highly ordered gold nanostructure arrays (NSA) prepared by thermally annealed island film and nanoimprint lithography (NIL) techniques, respectively. Each substrate possesses different morphology in terms of plasmonic enhancement. Both methods allow such important features as spectral tuning of plasmon resonance position depending on size and shape of nanostructures; however, the time and cost is quite different. The respective comparison was performed experimentally and theoretically for a number of samples with different geometrical parameters. Spectral characteristics of fabricated NSA exhibited an expressed plasmon peak in the range from 576 to 809 nm for thermally annealed samples and from 606 to 783 nm for samples prepared by NIL. Modelling of the optical response for nanostructures with typical shapes associated with these techniques (parallelepiped for NIL and semi-ellipsoid for annealed island films) was performed using finite-difference time-domain calculations. Mathematical simulations have indicated the dependence of electric field enhancement on the shape and size of the nanoparticles. As an important point, the distribution of electric field at so-called ‘hot spots’ was considered. Parallelepiped-shaped nanoparticles were shown to yield maximal enhancement values by an order of magnitude greater than their semi-ellipsoid-shaped counterparts; however, both nanoparticle shapes have demonstrated comparable effective electrical field enhancement values. Optimized Au nanostructures with equivalent diameters ranging from 85 to 143 nm and height equal to 35 nm were obtained for both techniques, resulting in the largest electrical field enhancement. The application of island film thermal annealing method for nanochips fabrication can be considered as a possible cost-effective platform for various surface-enhanced spectroscopies; while the NIL-fabricated NSA looks like more effective for sensing of small-size objects.
doi:10.1186/s11671-015-0819-1
PMCID: PMC4385248  PMID: 25852395
Localized surface plasmon resonance; Nanostructures; Annealed island films; Nanoimprint lithography; Plasmonic enhancement; 81.07.-b; 73.20.Mf

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