Table of contents

We present here a bottom-up approach for realizing on-chip on-demand batteries starting out with chemical vapor deposition-grown graphene. Single graphene monolayers contacted by electrode lines on a silicon chip serve as electrodes. The anode and cathode are realized by electrodeposition of zinc and copper respectively onto graphene, leading to the realization of a miniature graphene-based Daniell cell on a chip. The electrolyte is housed partly in a gel and partly in liquid form in an on-chip enclosure molded using a 3d printer or made out of poly(dimethylsiloxane). The realized batteries provide a stable voltage (∼1.1 V) for many hours and exhibit capacities as high as 15 μAh, providing enough power to operate a pocket calculator. The realized batteries show promise for deployment as on-chip power sources for autonomous systems in lab-on-a-chip or biomedical applications.

Research on graphene (Gr) is a vastly expanding field due to its potential for technological applications. Its close structural and chemical relationship to conjugated organic molecules makes it a superior candidate as a transparent electrode material in organic electronics and optoelectronics. The growth of organic thin films—intensively investigated in the past few decades—has demonstrated the complexity in growth and nucleation processes arising from the anisotropy and spatial extension of the molecular building blocks. Choosing the small, conjugated rod-like molecules para-hexaphenyl and pentacene as model representatives for small organic molecules, we review recent findings in organic thin film growth on a variety of Gr substrates. Special attention is paid to the differences in the resulting growth arising from the various methods of Gr fabrication and support that affect both the Gr–molecule interfacing and the involved molecular diffusion processes.

Quasi three-dimensional (3D) plasmonic nanostructures consisting of Au nanosquares on top of SU-8 nanopillars and Au nanoholes on the bottom were developed and fabricated using nanoimprint lithography with simultaneous thermal and UV exposure. These 3D plasmonic nanostructures were used to detect cell concentration of lung cancer A549 cells, retinal pigment epithelial (RPE) cells, and breast cancer MCF-7 cells. Nanoimprint technology has the advantage of producing high uniformity plasmonic nanostructures for such biosensors. Multiple resonance modes were observed in these quasi 3D plasmonic nanostructures. The hybrid coupling of localized surface plasmon resonances and Fabry–Perot cavity modes in the quasi 3D nanostructures resulted in high sensitivity of 496 nm/refractive index unit. The plasmonic resonance peak wavelength and sensitivity could be tuned by varying the Au thickness. Resonance peak shifts for different cells at the same concentration were distinct due to their different cell area and confluency. The cell concentration detection limit covered a large range of 5 × 10² to 1 × 10⁷ cells ml⁻¹ with these new plasmonic nanostructures. They also provide a large resonance peak shift of 51 nm for as little as 0.08 cells mm⁻² of RPE cells for high sensitivity cell detection.

Since transparent conducting films based on silver nanowires (AgNWs) have shown higher transmittance and electrical conductivity compared to those of indium tin oxide (ITO) films, the electronics industry has recognized them as promising substitutes. However, due to the higher haze value of AgNW transparent conducting films compared to ITO films, the clarity is decreased when AgNW films are applied to optoelectronic devices. In this study, we develop a highly transparent, low-haze, very long AgNW percolation network. Moreover, we confirm that analyzed chemical roles can easily be applied to different AgNW synthesis methods, and that they have a direct impact on the nanowire shape. Consequently, the lengths of the wires are increased up to 200 μm and the diameters of the wires are decreased up to 45 nm. Using these results, we fabricate highly transparent (96%) conductors (100 Ω/sq) with low-haze (2%) without any annealing process. This electrode shows enhanced clarity compared to previous results due to the decreased diffusive transmittance and scattering. In addition, a flexible touchscreen using a AgNW network is demonstrated to show the performance of modified AgNWs.

A novel type of aqueous fluorescent carbon dot (CD) was synthesized using citric acid as the only carbon source via an ammonium hydroxide modulated method, providing a blue color gamut. The amino group is considered to be the key factor in the high fluorescence of CDs and a model is established to investigate the mechanism of fluorescence. In addition, white light-emitting diodes (WLEDs) are fabricated by utilizing the prepared CDs and rare earth luminescent materials (SrSi₂O₂N₂:Eu and Sr₂Si₅N₈:Eu) as color conversion layers and UV-LED chips as the excitation light source. The WLEDs produce bright white light with attractive color rendering properties including a color rendering index of up to 95.1, a CIE coordinate of (0.33, 0.37), and a T_c of 5447 K under a 100 mA driven current, indicating that the CDs are promising in the field of optoelectronic devices.

A highly stable experimental setup was developed for the measurement of shot noise in atomic contacts and molecular junctions to determine the number of atoms or molecules present. The use of a nano-fabricated mechanically controllable break junction (MCBJ) electrode improved the overall stability of the experimental setup. The improved stability of the system and optimization of measurement system enabled us to comprehensively investigate the shot noise as well as charge transport properties in Au atomic contacts and molecular junctions. We present a solid proof that the number of atoms (cross sectional atom) in the Au atomic contacts was exactly one. In the atomic contacts, contribution from the additional channels was under the detection limit. Furthermore, the effect of molecular adsorption on the charge transport in the Au atomic contact was investigated. Additional transport channels were opened by exposing pyrazine molecules to the Au contacts, which gave rise to an increase in the Fano factor in the shot noise.

We show that ultrathin GaN membranes, with a thickness of 15 nm and planar dimensions of 12 × 184 μm², act as memristive devices. The memristive behavior is due to the migration of the negatively-charged deep traps, which form in the volume of the membrane during the fabrication process, towards the unoccupied surface states of the suspended membranes. The time constant of the migration process is of the order of tens of seconds and varies with the current or voltage sweep.

This paper presents the fabrication methodology of a linear variable photonic crystal (PC) filter with narrowband reflection that varies over a broad spectral range along the length of the filter. The key component of the linear variable PC filter is a polymer surface-relief grating whose period changes linearly as a function of its position on the filter. The grating is fabricated using a nanoreplica molding process with a wedge-shaped elastomer mold. The top surface of the mold carries the grating pattern and the wedge is formed by a shallow angle between the top and bottom surfaces of the mold. During the replica molding process, a uniaxial force is applied to stretch the mold, resulting in a nearly linearly varying grating period. The period of the grating is determined using the magnitude of the force and the local thickness of the mold. The grating period of the fabricated device spans a range of 421.8–463.3 nm over a distance of 20 mm. A high refractive index dielectric film is deposited on the graded-period grating to act as the waveguide layer of the PC device. The resonance reflection feature of the device varies linearly in a range of 680.2–737.0 nm over the length of the grating.

We developed a fabrication process for embedding a dense array (10⁸ cm⁻²) of high-aspect-ratio silicon nanowires (200 nm diameter and 10 μm tall) in a dielectric matrix and then structured/exposed the tips of the nanowires to form self-aligned gate field emitter arrays using chemical mechanical polishing (CMP). Using this structure, we demonstrated a high current density (100 A cm⁻²), uniform, and long lifetime (>100 h) silicon field emitter array architecture in which the current emitted by each tip is regulated by the silicon nanowire current limiter connected in series with the tip. Using the current voltage characteristics and with the aid of numerical device models, we estimated the tip radius of our field emission arrays to be ≈4.8 nm, as consistent with the tip radius measured using a scanning electron microscope (SEM).

Using the chemical vapour deposition method, we successfully converted smooth ZnO nanorods (NRs) into corrugated NRs by simply increasing the reaction time. The surface morphology and crystallographic structure of the corrugated NRs were investigated. The corrugated NRs were decorated by alternant $(11\bar{2}1)$ and $(11\bar{2}\bar{1})$ planes at the exposed side surfaces while the conventional $\{10\bar{1}0\}$ planes disappeared. No twinning boundaries were found in the periodically corrugated structures, indicating that they were type II corrugated NRs. Further investigation told us that they were selectively etched. We introduced a hydrothermal method to synthesize the smooth ZnO NRs and then etched them in a tube furnace at 950 °C with a flow of carbon monoxide. By separating the growth stage and the selective etching stage, we explicitly demonstrated a successfully selective etching effect on ZnO NRs with a carbon monoxide reducing atmosphere for the first time. An etching mechanism based on the selective reaction between carbon monoxide and the different exposed surfaces was proposed. Our results will improve the understanding of the growth mechanism on coarse or corrugated NRs and provide a new strategy for the application of surface controlled nanostructured materials.

pH was used as the main driving parameter for specifically immobilizing silicon nanowires onto Si₃N₄ microsquares at the surface of a SiO₂ substrate. Different pH values of the coating aqueous solution enabled to experimentally distribute nanowires between silicon nitride and silicon dioxide: at pH 3 nanowires were mainly anchored on Si₃N₄; they were evenly distributed between SiO₂ and Si₃N₄ at pH 2.8; and they were mainly anchored on SiO₂ at pH 2. A theoretical model based on DLVO theory and surface protonation/deprotonation equilibria was used to study how, in adequate pH conditions, Si nanowires could be anchored onto specific regions of a patterned Si₃N₄/SiO₂ surface. Instead of using capillary forces, or hydrophilic/hydrophobic contrast between the two types of materials, the specificity of immobilization could rely on surface electric charge contrasts between Si₃N₄ and SiO₂. This simple and generic method could be used for addressing a large diversity of nano-objects onto patterned substrates.

Typical thermostable and flexible polyimide polymers exhibit many excellent properties such as strong mechanical and chemical resistance. However, in contrast to single-crystal substrates like silicon or sapphire, polymers mostly display disordered and rough surfaces, which may result in instability and degradation of the interfaces between thin films and polymer substrates. As a step toward the development of next-generation polymer substrates, we here report single-atom-layer imprinting onto the polyimide sheets, resulting in an ultrasmooth 0.3 nm high atomic step-and-terrace surface on the polyimides. The ultrasmooth polymer substrates are expected to be applied to the fabrication of nanostructures such as superlattices, nanowires, or quantum dots in nanoscale-controlled electronic devices. We fabricate smooth and atomically stepped indium tin oxide transparent conducting oxide thin films on the imprinted polyimide sheets for future use in organic-based optoelectronic devices processed with nanoscale precision. Furthermore, toward 2D polymer substrate nanoengineering, we demonstrate nanoscale letter writing on the atomic step-and-terrace polyimide surface via atomic force microscopy probe scratching.

Colloidal quantum dots have attracted significant interest in recent years for lighting and display applications and have recently appeared in high-end market products. The integration of quantum dots with light emitting diodes has made them promising candidates for superior lighting applications with tunable optical characteristics. In this work we propose and demonstrate high quality colloidal quantum dots in their novel free-standing film forms to allow high quality white light generation to address flexible lighting and display applications. High quality quantum dots have been characterized using transmission electron microscopy, x-ray diffraction, x-ray photoelectron spectroscopy, steady state and time resolved photoluminescence and dynamic light scattering methods. The engineering of colloidal quantum dot composition and its optical properties in stand-alone film form has led to the experimentally high NTSC color gamut of 122.5 (CIE-1931) for display applications, color rendering index of 88.6, luminous efficacy of optical radiation value of 290 lm/W_opt and color temperature of 2763 K for lighting applications.

The paper presents the growth of hexagonal NaYF₄:Yb³⁺, Tm³⁺ nanocrystals with tunable sizes induced by different contents of doped Yb³⁺ ions (10%–99.5%) using the thermal decomposition method. These nanoparticles, which have different sizes, are then self-assembled at the interface of cyclohexane and ethylene and transferred onto a normal glass slide. It is found that the size of nanoparticles directs their self-assembly. Due to the appropriate size of 40.5 nm, 15% Yb³⁺ ions doped nanoparticles are able to be self-assembled into an ordered inorganic monolayer membrane with a large area of about 10 × 10 μm². More importantly, the obvious short-wave (300–500 nm) fluorescence improvement of the ordered 2D self-assembly structure is observed to be relative to disordered nanoparticles, which is because intrinsic absorption and scattering of upconversion nanoparticles leads to the self-loss of fluorescence, especially the short-wave fluorescence inside the disordered structure, and the relative emission of short-wave fluorescence is reduced. The construction of a 2D self-assembly structure can effectively avoid this and improve the radiated short-wave fluorescence, especially UV photons, and is able to direct the design of new types of solid-state optical materials in many fields.

Silver nanobelts are demonstrated here to undergo inter-particle joining at relatively low temperatures of less than 180 °C. For surface-coated networks of nanobelts this joining reduced the network sheet resistance by 95%. The joining mechanism appears to be non-diffusional oriented attachment, caused by the thermal reactivation of the halted oriented attachment mechanism that occurred originally at room temperature during the rapid nanobelt synthesis. This self-assembly mechanism was explored by in situ electrical and calorimetric experiments, and supported by electron microscopy. Unlike pentagonal silver nanowires, silver nanobelts do not rely on diffusional instability to achieve workably low joining temperatures. The oriented attachment displayed by nanobelts represents a new approach to achieving valuable reductions in network resistance, disentangled from the instability and diffusion-driven failure by nanoparticle degradation displayed by competing silver nanoparticles.

Despite the current interest in the scientific community in exploiting divergent surface properties of graphitic carbon allotropes, conclusive differentiation remains elusive even when dealing with parameters as fundamental as adhesion. Here, we set out to provide conclusive experimental evidence on the time evolution of the surface properties of highly oriented pyrolytic graphite (HOPG), graphene monolayer (GML) and multiwalled carbon nanotubes (MWCNTs) as we expose these materials to airborne contaminants, by providing (1) statistically significant results based on large datasets consisting of thousands of force measurements, and (2) errors sufficiently self-consistent to treat the comparison between datasets in atomic force microscopy (AFM) measurements. We first consider HOPG as a model system and then employ our results to draw conclusions from the GML and MWCNT samples. We find that the surface properties of aged HOPG are indistinguishable from those of aged GML and MWCNT, while being distinct from those of cleaved HOPG. Herein, we provide a sufficient body of evidence to disregard any divergence in surface properties for multidimensional sp² carbon allotropes that undergo similar aging processes.

We report optical properties of iron pyrite (FeS₂) determined from ex situ spectroscopic ellipsometry measurements made on both a commercially available bulk single crystal and nanocrystalline thin film over a spectral range of 0.735–5.887 eV. The complex dielectric function, ε (E) = ε₁ (E) + iε₂ (E), spectra have been determined by fitting a layered parametric model to the ellipsometric measurements. Spectra in ε are modeled using a Kramers–Kronig consistent critical point parabolic band model involving seven critical points for the bulk single crystal and four critical points for the nanocrystalline film. Absorption coefficient spectra for both types of samples are also determined from ε. Critical point features in the nanocrystalline films are broader, have lower amplitude and lower energy critical points detected having a small blue shift when compared to the single crystal sample.

Bicrystalline α-Fe₂O₃ nanoblades (NBs) synthesized by thermal oxidation of iron foils were reduced in vacuum, to study the effect of reduction treatment on microstructural changes and photocatalytic properties. After the vacuum reduction, most bicrystalline α-Fe₂O₃ NBs transform into single-layered NBs, which contain more defects such as oxygen vacancies, perfect dislocations and dense pores. By comparing the photodegradation capability of non-reduced and reduced α-Fe₂O₃ NBs over model dye rhodamine B (RhB) in the presence of hydrogen peroxide, we find that vacuum-reduction induced microstructural defects can significantly enhance the photocatalytic efficiency. Even after 10 cycles, the reduced α-Fe₂O₃ NBs still show a very high photocatalytic activity. Our results demonstrate that defect engineering is a powerful tool to enhance the photocatalytic performance of nanomaterials.

The interface trap density in single-walled carbon nanotube (SWNT) network thin-film transistors (TFTs) is a fundamental and important parameter for assessing the electronic performance of TFTs. However, the number of studies on the extraction of interface trap densities, particularly in SWNT TFTs, has been insufficient. In this work, we propose an efficient technique for extracting the energy-dependent interface traps in SWNT TFTs. From the measured dispersive, frequency-dependent capacitance–voltage (C–V) characteristics, the dispersive-free, frequency-independent C–V curve was obtained, thus enabling the extraction and analysis of the interface trap density, which was found to be approximately 8.2 × 10¹¹ eV⁻¹ cm⁻² at the valence band edge. The frequency-independent C–V curve also allows further extraction of the quantum capacitance in the SWNT network without introducing any additional fitting process or parameters. We found that the extracted value of the quantum capacitance in SWNT networks is lower than the theoretical value in aligned SWNTs due to the cross point of SWNTs on the SWNT network. Therefore, the method proposed in this work indicates that the C–V measurement is a powerful tool for obtaining deep physical insights regarding the electrical performance of SWNT TFTs.

By fabricating CoFeB/MgO/CoFeB-based perpendicular-magnetic tunnel junction (p-MTJ) spin-valves stacked with a [Co/Pd]_n-SyAF layer based on a TiN bottom electrode on a 12 inch Si wafer (001) substrate, we investigated how the bridging layers of Ta, Ti, and Pt and their thickness variation affected the tunneling magneto-resistance (TMR) ratio of Co₂Fe₆B₂ pinned-layer behavior in magnetic-tunnel-junctions. TMR ratios for Ta, Ti, and Pt bridging layers were observed to be 64.1, 70.2, and 29.5%, respectively. It was confirmed by high resolution transmission electron microscopy (HR-TEM) that this difference resulted from CoFeB/MgO/CoFeB MTJ layers with Ta and Ti bridging layers being textured well with a bcc (100) structure, indicating that Ta and Ti bridging layers bridged SyAF fcc (111) and MTJ bcc (100). On the other hand, the MTJ layer with Pt bridging layer was incorrectly textured, indicating that a Pt bridging layer is unsuitable to bridge SyAF fcc (111) and MTJ bcc (100) due to Pt being diffused into the CoFeB pinned-layer. In addition, perpendicular magnetic anisotropy (PMA) behavior of the CoFeB pinned-layer was found to depend strongly on a bridging layer thickness; higher TMRs of Ta and Ti were observed at the optimal bridging layers' thickness, which enable the realization of PMAs of the pinned-layer and ferro-coupling of the pinned-layer with the lower-SyAF layer. Among the three bridging materials (Ta, Ti, and Pt), we observed that Ti showed the highest TMR ratio and widest thickness range for a high TMR ratio, indicating that a higher TMR ratio is needed to obtain the best deposition process margin.

Dependences of gas-barrier performance on the deposition temperature of atomic-layer-deposited (ALD) Al₂O₃, HfO₂, and ZnO films were studied to establish low-temperature ALD processes for encapsulating organic light-emitting diodes (OLEDs). By identifying and controlling the key factors, i.e. using H₂O₂ as an oxidant, laminating Al₂O₃ with HfO₂ or ZnO layers into AHO or AZO nanolaminates, and extending purge steps, OLED-acceptable gas-barrier performance (water vapor transmission rates ∼ 10⁻⁶ g m⁻² d⁻¹) was achieved for the first time at a low deposition temperature of 50 °C in a thermal ALD mode. The compatibility of the low-temperature ALD process with OLEDs was confirmed by applying the process to encapsulate different types of OLED devices, which were degradation-free upon encapsulation and showed adequate lifetime during accelerated aging tests (pixel shrinkage <5% after 240 h at 60 °C/90% RH).