Table of contents

We present a novel method of radio frequency (RF)-mediated thermotherapy in tumors by remotely heating nickel (Ni)–gold (Au) core–shell nanowires (CSNWs). Ectopic pancreatic tumors were developed in nude mice to evaluate the thermotherapeutic effects on tumor progression. Tumor ablation was produced by RF-mediated thermotherapy via activation of the paramagnetic properties of the Ni–Au CSNWs. Histopathology demonstrated that heat generated by RF irradiation caused significant cellular death with pyknotic nuclei and nuclear fragmentation dispersed throughout the tumors. These preliminary results suggest that thermotherapy ablation induced via RF activation of nanowires provides a potential alternative therapy for cancer treatment.

Photoinitiator-free fabrication of poly(ethylene glycol) diacrylate (PEGDA) scaffolds is achieved using a novel three-dimensional (3D) printing method called mask projected excimer laser stereolithography (MPExSL). The spatial resolution of photoinitiator-free curing is suitable for 3D layer-by-layer fabrication with a single layer thickness well controllable at tens to hundreds of microns using 248 nm wavelength for the irradiation. The photoinitiator-free scaffolds are superior compared to their counterparts fabricated by using photoinitiator molecules, showing a higher level of biocompatibility. A release of toxic chemicals from the photoinitiator containing scaffolds is proven by cell proliferation tests. In contrast, no toxic release is found from the photoinitiator-free scaffolds, resulting in the very same level of cell proliferation as the control sample. The demonstration of photoinitiator-free PEGDA scaffolds enables the fabrication of 3D scaffolds with the highest level of biocompatibility for both in vitro and in vivo applications.

Light-activated theranostic materials offer a potential platform for optical imaging and phototherapeutic applications. We have engineered constructs derived from erythrocytes, which can be doped with the FDA-approved near infrared (NIR) chromophore, indocyanine green (ICG). We refer to these constructs as NIR erythrocyte-mimicking transducers (NETs). Herein, we investigated the effects of changing the NETs mean diameter from micron- (≈4 μm) to nano- (≈90 nm) scale, and the ICG concentration utilized in the fabrication of NETs from 5 to 20 μM on the resulting absorption and scattering characteristics of the NETs. Our approach consisted of integrating sphere-based measurements of light transmittance and reflectance, and subsequent utilization of these measurements in an inverse adding-doubling algorithm to estimate the absorption (μ_a) and reduced scattering (μ_s') coefficients of these NETs. For a given NETs diameter, values of μ_a increased over the approximate spectral band of 630–860 nm with increasing ICG concentration. Micron-sized NETs produced the highest peak value of μ_a when using ICG concentrations of 10 and 20 μM, and showed increased values of μ_s' as compared to nano-sized NETs. Spectral profiles of μ_s' for these NETs showed a trend consistent with Mie scattering behavior for spherical objects. For all NETs investigated, changing the ICG concentration minimally affected the scattering characteristics. A Monte Carlo-based model of light distribution showed that the presence of these NETs enhanced the fluence levels within simulated blood vessels. These results provide important data towards determining the appropriate light dosimetry parameters for an intended light-based biomedical application of NETs.

TiO₂ microspheres (TMSs) with unique hierarchical structure and unusual high specific surface area are synthesized and incorporated into a photoanode in various TMS multilayer gradient architectures to form novel photoanodes and dye-sensitized solar cells (DSSCs). Significant influences of these architectures on the photoelectric properties of DSSCs are obtained. The DSSC with the optimal TMS gradient-ascent architecture of M036 has the largest amounts of dye absorption, strongest light absorption, longest electron lifetime and lowest electron recombination, and thus exhibits the maximum short circuit current density (J_sc) of 16.49 mA cm⁻² and photoelectric conversion efficiency (η) of 7.01%, notably higher than those of conventional DSSCs by 21% and 22%, respectively. These notable improvements in the properties of DSSCs can be attributed to the TMS gradient-ascent architecture of M036 which can most effectively increase dye absorption and localize incident light within the photoanode by the light scattering of TMSs, and thus utilize the incident light thoroughly. This study provides an optimized and universal configuration for the scattering microspheres incorporated in the hybrid photoanode, which can significantly improve the performance of DSSCs.

The scaling potential of 'mushroom-type' phase-change memory devices is evaluated, down to single-nanometre dimensions, using physically realistic simulations that combine electro-thermal modelling with a Gillespie Cellular Automata phase-transformation approach. We found that cells with heater contact sizes as small as 6 nm could be successfully amorphized and re-crystallized (RESET and SET) using moderate excitation voltages. However, to enable the efficient formation of amorphous domes during RESET in small cells (heater contact diameters of 10 nm or less), it was necessary to improve the thermal confinement of the cell to reduce heat loss via the electrodes. The resistance window between the SET and RESET states decreased as the cell size reduced, but it was still more than an order of magnitude even for the smallest cells. As expected, the RESET current reduced as the cells got smaller; indeed, RESET current scaled with the inverse of the heater contact diameter and ultra-small RESET currents of only 19 μA were achieved for the smallest cells. Our results show that the conventional mushroom-type phase-change cell architecture is scalable and operable in the sub-10nm region.

Copper (Cu) films and circuits were fabricated by screen-printing Cu nanoink on low-Tg (glass transition temperature) flexible plastic substrates (PEN and PET) instead of widely used high-Tg polyimide (PI) substrate. Photonic sintering of printed Cu films was carried out using intensive pulsed light (IPL). Low resistivities of 28 μΩ · cm on PEN and 44 μΩ · cm on PET were obtained without damaging the substrates. The sintered Cu films exhibited strong adhesion to PEN and PET substrates, with measured adhesion strength of 5B by the ASTM D3359 international standard, whereas the top part of the copper film on the PI substrate was stripped off during the adhesion test. The sintered Cu films also showed excellent stability in harsh conditions and mechanical flexibility in rolling tests. The underlying mechanisms of the high conductivity and strong adhesion on PEN and PET substrates with low-energy IPL sintering were investigated. Simple circuits and radio frequency identification antennas were made by screen-printing Cu nanoink and IPL sintering, demonstrating the technique's feasibility for practical applications.

The surface orientation of metal nanoparticles is critical to their physical and chemical properties. This study aims on the understanding of the effect of surface orientation as well as heterogeneous epitaxy of metal nanoparticles at an interface between two materials with a large lattice mismatch. Silver nanoparticles of different diameters were grown on arrays of calcium fluoride (CaF₂) nanorods using oblique angle deposition as a model system for this study. Scanning electron microscopy and transmission electron microscopy (TEM) imaging were used to verify that the nanoparticles were selectively grown on the desired {111} facets of the nanorod tips. Using selected area diffraction and dark field imaging in TEM, it was shown that the nanoparticles were grown at a (111) orientation at the CaF₂ interface with large lattice strains. Thus biaxially textured CaF₂ nanorod arrays can be used as a catalytic support.

One of the main challenges in plasmonics is to conceive large-scale, low-cost techniques suitable for the fabrication of metal nanoparticle patterns showing precise spatial organization. Here, we introduce a simple method based on continuous-wave laser illumination to induce the self-organization of silver nanoparticles within high-index thin films. We show that highly regular and homogeneous nanoparticle gratings can be produced on large areas using laser-controlled self-organization processes. This very versatile technique can provide 1D and 2D patterns at a subwavelength scale with tunable features. It does not need any stabilization or expensive devices, such as those required by optical or electron lithography, and is rapid to implement. Accurate in-plane and in-depth characterizations provide valuable information to explain the mechanisms that lead to pattern formation and especially how 2D self-organization can fall into place with successive laser scans. The regular and homogeneous 2D self-organization of metallic NPs with a single laser scan is also reported for the first time in this article. As the reported nanostructures are embedded in porous TiO₂, we also theoretically explore the interesting potential of organization on the photocatalytic activity of Ag-NP-containing TiO₂ porous films, which is one of the most promising materials for self-cleaning or remediation applications. Realistic electromagnetic simulations demonstrate that the periodic organization of silver nanoparticles can increase the light intensity within the film more than ten times that produced with randomly distributed nanoparticles, leading as expected to enhanced photocatalytic efficiency.

The mechanism of upconversion at the nanoscale is still under discussion. In this paper, we report on the experimental results of anti-Stokes luminescence kinetics in the upconversion nanoparticles of β-NaYF₄: 20%Yb³⁺; 0.6%Tm³⁺. The parameters of the luminescence kinetics were found to be unambiguously dependent on the number of excitation quanta n, which are necessary for certain transitions between the energy states of thulium ions. The observed correlation has been explained by means of the long-lasting energy migration between the ytterbium ions. The spread in time between the luminescent maxima of the corresponding thulium transitions not only shows the nonlinear character of upconversion, but also reveals the time scale of energy migration as well. From these, we derive that the conventional Förster formalism applied to the estimation of energy transfer efficiency in UCNP-fluorophore pairs can provide misleading results.

We investigated the ultraviolet (UV) responses of a heterojunction Si quantum dot (QD) solar cell consisting of p-type Si-QDs fabricated on a n-type crystalline Si (p-Si-QD/n-c-Si HJSC). The UV responses were compared with a conventional n-type crystalline Si solar cell (n-c-Si SC). The external and internal quantum efficiency results of the p-Si-QD/n-c-Si HJSC exhibited a clear enhancement in the UV responses (300–400 nm), which was not observed in the n-c-Si SC. Based on the results of the cell reflectance and bias-dependent responses, we expect that almost all UV responses occur in the p-Si-QD layer, and the generated carriers can be transported via the Si-QD layer due to the formation of a sufficient electric filed. As a result, a high power conversion efficiency of 14.5% was achieved from the p-Si-QD/n-c-Si HJSC. By reducing the thickness of the n-Si substrate from 650 μm to 300 μm, more enhanced power conversion efficiency of 14.8% was obtained which is the highest value among the reported Si-QD based solar cells to date.

Hole collection and transport are crucial physical processes in bulk-heterojunction (BHJ) solar cells, which represent major bottlenecks due to their limitations in power conversion efficiency (PCE). Hence, a more efficient alternative is needed to accept and transport holes to the collection electrode in BHJ solar cells. Here, we bring both electron and hole collection centres close to the point of exciton generation by infiltrating P3HT poly(3-hexylthiophene):PCBM ([6,6]-phenyl-C61-butyric acid methyl ester) blend into a highly porous interconnected p-type NiO-nanoparticle (NiO-np) network, through solvent-assisted grafting. In this study, a hybrid polymer solar cell is demonstrated with a P3HT:PCBM:NiO-np triple-heterojunction active layer which showed greatly improved rectification behaviour, long electron lifetime and generated higher PCE of 4% under AM 1.5 solar illumination with a 75% increase in PCE with respect to the P3HT:PCBM device. The optimum NiO-np amount and active-layer thickness were found to be 2% and 250 nm, respectively.

In this work, thermal transport at the junction of an asymmetric layer hexagonal boron-nitride (h-BN) heterostructure is explored using a non-equilibrium molecular dynamics method. A thermal contact resistance of 3.6 × 10⁻¹¹ K · m² W⁻¹ is characterized at a temperature of 300 K with heat flux from the trilayer to monolayer regions. The mismatch in the flexural phonon modes revealed by power spectra analysis provides the driving force for the calculated thermal resistance. A high thermal rectification efficiency of 360% is calculated at the layer junction surpassing that of graphene. Several modulators, i.e. the system temperature, contact pressure and lateral dimensions, are applied to manipulate the thermal conductance and rectification across the interfaces. The predicted thermal rectification sustains positive correlations with temperature and phonon propagation lengths with little change to the coupling strength.

Polyethylene terephthalate (PET) films' electret property was significantly enhanced after being treated with inductively coupled plasma (ICP). Based on this modified material, the triboelectric nanogenerators' (TENGs) transferred charges remained at 68.6% of the initial value after 400 000 cycles of contact-separation process, which was about three times that of the untreated samples.

We investigated the gas sensing characteristics of graphene nanosheet (NS)-loaded SnO₂ nanofibers (NFs) that were synthesized by a low-cost facile electrospinning process. The sensing performance was characterized as a function of the graphene content with various gases such as C₆H₆, C₇H₈, CO, CO₂, and H₂S. The loading of graphene NSs significantly improved the gas sensing performances of SnO₂ NFs. The optimal amount of graphene NSs was found to be 0.5 wt%. We proposed a sensing mechanism for the enhanced sensing performance based on the chemical sensitization of graphene NSs and the charge transfer through the heterointerfaces between graphene NSs and SnO₂ nanograins. The results show that graphene NS-loaded SnO₂ NFs are a promising sensing material system that can detect hazardous gaseous species.

The gas response of single-wall carbon nanotubes (SWCNT) functionalized with indium tin oxide (ITO) nanoparticles (NP) has been studied at room temperature and an enhanced sensitivity to ammonia and nitrogen dioxide is demonstrated. The higher sensitivity in the functionalized sample is related to the creation of nano-heterojunctions at the interface between SWCNT bundles and ITO NP. Furthermore, the different response of the two devices upon NO₂ exposure provides a way to enhance also the selectivity. This behavior is rationalized by considering a gas sensing mechanism based on the build-up of space-charge layers at the junctions. Finally, full recovery of the signal after exposure to NO₂ is achieved by UV irradiation for the functionalized sample, where the ITO NP can play a role to hinder the poisoning effects on SWCNT due to NO₂ chemisorption.

In this work, highly luminescent quaternary CuNiInS nanocrystals (NCs) are put forward as a good prototype for investigating defect-induced room temperature ferromagnetism. A ferromagnetic Ni cation can preserve the strong luminescence of NCs without introducing intermediate energy levels in the center of the forbidden band. The strong luminescence of NCs is used as an indicator for monitoring the concentration of vacancy defects inside them, facilitating the investigation of the origin of room temperature ferromagnetism in CuNiInS NCs. Our results reveal that the patching of Cu vacancies $({{{\rm{V}}}_{{\rm{Cu}}}}^{-})$ with Ni will result in bound magnetic polarons composed of both ${{{\rm{V}}}_{{\rm{Cu}}}}^{-}$ and a substitution of Cu by Ni $({{{\rm{Ni}}}_{{\rm{Cu}}}}^{+}),$ giving rise to the room temperature ferromagnetism of CuNiInS NCs. Either the ferromagnetic Ni or the non-ferromagnetic Cu cation can tune the magnetism of CuNiInS NCs because of the change of bound magnetic polaron concentration at the altered concentration ratio of ${{{\rm{V}}}_{{\rm{Cu}}}}^{-}$ and ${{{\rm{Ni}}}_{{\rm{Cu}}}}^{+}$.

We report a systematic study of the controlled gas-phase synthesis of silver–silica hybrid nanostructures (Ag-SiO₂ NP) using the concept of evaporation-induced self-assembly. The approach includes the use of a direct gas-phase electrophoresis for size classification and in situ characterization of mobility size. Transmission electron microscopy and ultraviolet-visible light spectroscopy were employed complementarily to determine the morphology and surface plasmon resonance of Ag-SiO₂ NP. Results show that two types of Ag-SiO₂ NPs were successfully synthesized: (1) AgNPs decorated on a SiO₂-NP (Ag-T-SiO₂ NP), and (2) AgNPs doped in a cluster of SiO₂-NPs (Ag-C-SiO₂ NP). The physical size, morphology, and compositions of Ag-SiO₂ NPs were tunable through the adjustments of precursor concentrations and the selected mobility sizes. The results also show that SPR performance, colloidal stability, and dispersibility of AgNPs enhanced significantly in an aqueous environment after the hybridization with SiO₂-NP (especially for Ag-C-SiO₂ NP). The results and corresponding methodology summarized here provide the proof of concept to fabricate high-purity AgNP-based hybrid nanostructures through gas-phase evaporation-induced self-assembly for future biomedical applications (e.g., hyperthermal therapy, targeted drug delivery, and antibacterial applications).

We present a study on the formation of p-type ZnO thin film through ion implantation. Group V dopants (N, P) with different ionic radii are implanted into chemical vapor deposition grown ZnO thin film on GaN/sapphire substrates prior to thermal activation. It is found that mono-doped ZnO by N⁺ implantation results in n-type conductivity under thermal activation. Dual-doped ZnO film with a N:P ion implantation dose ratio of 4:1 is found to be p-type under certain thermal activation conditions. Higher p-type activation levels (10¹⁹ cm⁻³) under a wider thermal activation range are found for the N/P dual-doped ZnO film co-implanted by additional oxygen ions. From high resolution x-ray diffraction and x-ray photoelectron spectroscopy it is concluded that the observed p-type conductivities are a result of the promoted formation of P_Zn–4N_O complex defects via the concurrent substitution of nitrogen at oxygen sites and phosphorus at zinc sites. The enhanced solubility and stability of acceptor defects in oxygen co-implanted dual-doped ZnO film are related to the reduction of oxygen vacancy defects at the surface. Our study demonstrates the prospect of the formation of stable p-type ZnO film through co-implantation.

This work demonstrates that thin-walled platinum nanotubes can be readily synthesized by controlling the interfacial double layer in alumina nanochannels. The gradient distribution of ions in nanochannels enables the creation of Pt nanotubes with walls as thin as 5 nm at the top end when using a solution containing polyvinylpyrrolidone (PVP) and chloroplatinic acid (H₂PtCl₆) under the influence of an electric potential in nanochannels. The highly efficient formation of thin-walled Pt nanotubes is a result of the concentration gradient of ${{{\rm{PtCl}}}_{6}}^{2-}$ and a thick double layer, which was caused by the low concentration of Pt precursors and the enhanced surface charge density induced by protonated PVP steric adsorption. This well-controlled synthesis reveals that the interfacial double layer is a useful tool to tailor the structure of nanomaterials in a nanoscale space, and holds promise in the construction of more complex functional nanostructures.

In nanoparticle systems consisting of two magnetic materials (bi-magnetic nanoparticles or nanoparticles embedded in a magnetic matrix), there is a constantly growing interest in the investigation of the interplay between interparticle interactions and the nanoparticle-matrix interface exchange coupling, because of its enormous impact on a number of technological applications. The understanding of the mechanisms of such interplay is a great challenge, as it would allow controlling equilibrium and non-equilibrium magnetization dynamics of exchange coupled nanoparticles systems and finely tuning their anisotropy. Here, we provide evidence that this interplay leads to a collective superspin glass (SSG) behavior in a system of diluted ferromagnetic (FM) nanoparticles embedded in an antiferromagnetic (AFM) matrix (5% volume fraction of Co particles in Mn film matrix). We have developed a novel mesoscopic model to study the influence of interparticle interaction on the exchange bias (EB) and the dynamical behavior of assemblies of FM nanoparticles embedded in a granular AFM matrix. Our mesoscopic model is based on reducing the amount of simulated spins to the minimum number necessary to describe the magnetic structure of the system and introducing the adequate exchange parameters between the different spins. The model replicates remarkably well the observed static and dynamical SSG properties as well as the EB behavior. In addition, the proposed model well explains the role of the significant Co/Mn alloying and of the granularity of the matrix in mediating interparticle interactions through exchange and dipole–dipole coupling between the uncompensated moments of its grains and the exchange interaction at the Co/Mn interface.

Large-scale electrorheology (ER) response has been reported for dilute graphene nanoflake-based ER fluids that have been engineered as novel, readily synthesizable polymeric gels. Polyethylene glycol (PEG 400) based graphene gels have been synthesized and a very high ER response (∼125 000% enhancement in viscosity under influence of an electric field) has been observed for low concentration systems (∼2 wt.%). The gels overcome several drawbacks innate to ER fluids. The gels exhibit long term stability, a high graphene packing ratio which ensures very high ER response, and the microstructure of the gels ensures that fibrillation of the graphene nanoflakes under an electric field is undisturbed by thermal fluctuations, further leading to mega ER. The gels exhibit a large yield stress handling caliber with a yield stress observed as high as ∼13 kPa at 2 wt.% for graphene. Detailed investigations on the effects of graphene concentration, electric field strength, imposed shear resistance, transients of electric field actuation on the ER response and ER hysteresis of the gels have been performed. In-depth analyses with explanations have been provided for the observations and effects, such as inter flake lubrication/slip induced augmented ER response. The present gels show great promise as potential ER gels for various smart applications.

Localization of atomic defect-induced electronic transport through a single graphene layer is calculated using a full-valence electronic structure description as a function of the defect density and taking into account the atomic-scale deformations of the layer. The elementary electronic destructive interferences leading to Anderson localization are analyzed. The low-voltage current intensity decreases with increasing length and defect density, with a calculated localization length ζ = 3.5 nm for a defect density of 5%. The difference from the experimental defect density of 0.5% required for an oxide surface-supported graphene to obtain the same ζ is discussed, pointing out how interactions of the graphene supporting surface and surface chemical modifications also control electronic transport localization.

Onion-like carbon nanospheres (OCNSs) with an average diameter of 43 nm were produced on a large scale via a combustion method and examined as an anode material for lithium ion batteries. The OCNSs exhibit a remarkable electrochemical cycling behavior and a capacity much higher than that of graphite. The capacity increases significantly with increasing charge–discharge cycles and reaches a value of 178% of the initial value (from 586 mA h g⁻¹to 1045 mA h g⁻¹) after 200 cycles. Further investigation provides unambiguous experimental evidence that such a remarkable capacity increase is related to the stable onion-like structure of the OCNSs and to the existence of large numbers of disordered/short graphitic fragments, which gradually provide more active sites for Li ion storage. The unique electrochemical performance of OCNSs provides a new way to design a high-performance anode material for rechargeable batteries.

Pure and cobalt-doped zinc oxide aligned nanorods have been grown by the low-temperature (90 °C) aqueous chemical method on amorphous ZnO seed layer, deposited on a sapphire substrate. High crystallinity of these objects is demonstrated by the electron paramagnetic resonance investigation at liquid helium temperature. The successful incorporation of Co²⁺ ions in substitution of Zn²⁺ ones in the ZnO matrix has also been confirmed. A drastic reduction of intrinsic ZnO nanorods core defects is observed in the Co-doped samples, which enhances the structural quality of the NRs. The quantification of substitutional Co²⁺ ions in the ZnO matrix is achieved by comparison with a reference sample. The findings in this study indicate the potential of using the low-temperature aqueous chemical approach for synthesizing material for spintronics applications.

The phonon energies of AlGaP in wurtzite crystal structure are generally not known, as opposed to their zincblende counterparts, because AlGaP crystallizes in zincblende phase in bulk and thin films structures. However, in nanowires AlGaP can be grown in wurtzite crystal structure. In this work we have grown wurtzite GaP/AlGaP/GaP core–shell nanowires by use of MOVPE. After developing suitable growth conditions, the Al composition was determined by STEM-EDX measurements and the wurtzite AlGaP phonon energies by Raman spectroscopy. Raman measurements show a peak shift with increasing Al composition in the AlGaP shell. We find that the phonon energies for wurtzite AlGaP are slightly lower than for zincblende AlGaP. Our results can be used to determine the Al composition in wurtzite AlGaP by Raman scattering.

Germanium nanocrystals (Ge-ncs) were synthesized by implantation of Ge⁺ ions into the fused silica, followed by a thermal annealing at 1000 °C. High-resolution transmission electron microscopy was employed to characterize both the morphology of the formed Ge-ncs and the evolution of their depth-distribution as a function of annealing durations. The formation of nanocavities in the vicinity of nanocrystal/SiO₂ interface is evidenced, as well as their influence on the release of the compressive stress exerted on Ge-ncs by surrounding SiO₂. Some Ge-ncs are found inside nanocavities, and can move into the implanted layer through a nanocavity-assisted diffusion mechanism. This finding sheds light on a new process that can explain the non-uniformity of the Ge-nanocrystal spatial distribution.