Table of contents

Imaging of high-aspect-ratio nanostructures with sharp edges and straight walls in nanoscale metrology by atomic force microscopy (AFM) has been challenging due to the mechanical properties and conical geometry of the majority of available commercial tips. Here we report on the fabrication of GaN probes for nanoscale metrology of high-aspect-ratio structures to enhance the resolution of AFM imaging and improve the durability of AFM tips. GaN nanowires were fabricated using bottom-up and top-down techniques and bonded to Si cantilevers to scan vertical trenches on Si substrates. Over several scans, the GaN probes demonstrated excellent durability while scanning uneven structures and showed resolution enhancements in topography images, independent of scan direction, compared to commercial Si tips.

Ultrathin Ni doped CoO_x films were prepared by direct current co-sputtering at room temperature as inorganic hole transport materials for inverted perovskite solar cells. P-type doping was designed to adjust the valence band position of CoO_x to match the that of CH₃NH₃PbI₃, which would effectively eliminate the interface barrier. Moreover, the hole extraction ability would be enhanced and the power conversion efficiency of the devices hence increased from 3.68% to 9.60%. The optimized performance was also accompanied by decent stability as a result of its intrinsic stability.

Energy density, safety, and simple and environmentally friendly preparation methods are very significant aspects in the realization of a compact supercapacitor. Herein we report the use of a supercritical CO₂-assisted gel drying process (SC-CO₂) for the preparation of porous electrodes containing dispersed graphene in a poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) binder membrane to sandwich in a new portable supercapacitor based on graphene oxide (GO). A GO loading of 60 wt.% was found to give the best combination of factors (porosity, wettability, mechanical and electrochemical properties). Cycling voltammetry and charge/discharge studies showed an excellent capacitance behaviour and stability in an ionic liquid electrolyte, suggesting SC-CO₂ processing as a promising platform to produce highly bulky and porous films for supercapacitors. The supercapacitor device delivers a very high energy density of 79.2 Wh kg⁻¹ at a power density of 0.23 KW kg⁻¹ (current density 0.5 A g⁻¹, specific capacitance 36.2 F g⁻¹) while that of steel remains at 50.3 Wh kg⁻¹ at a power density of 2.8 KW kg⁻¹ (current density 6 A g⁻¹, specific capacitance 23.5 F g⁻¹).

Efficient delivery of short interfering RNA (siRNA) remains one of the primary challenges of RNA interference therapy. Polyethylene glycol (PEG)ylated polycationic carriers have been widely used for the condensation of DNA and RNA molecules into complex-core micelles. The PEG corona of such nanoparticles can significantly improve their colloidal stability in serum, but PEGylation of the carriers also reduces their condensation capacity, hindering the generation of micellar particles with sufficient complex stability. This presents a particularly significant challenge for packaging siRNA into complex micelles, as it has a much smaller size and more rigid chain structure than DNA plasmids. Here, we report a new method to enhance the condensation of siRNA with PEGylated linear polyethylenimine using organic solvent and to prepare smaller siRNA nanoparticles with a more extended PEG corona and consequently higher stability. As a proof of principle, we have demonstrated the improved gene knockdown efficiency resulting from the reduced siRNA micelle size in mice livers following intravenous administration.

The influence of water vapor on the electronic property of MoS₂ field effect transistors (FETs) is studied through controlled experiments. We fabricate supported and suspended FETs on the same piece of MoS₂ to figure out the role of SiO₂ substrate on the water sensing property of MoS₂. The two kinds of devices show similar response to water vapor and to different treatments, such as pumping in the vacuum, annealing at 500 K and current annealing, indicating the substrate does not play an important role in the MoS₂ water sensor. Water adsorption is found to decrease the carrier mobility probably through introducing a scattering center on the surface of MoS₂. The threshold voltage and subthreshold swing of the FETs do not change obviously after introducing water vapor, indicating there is no obvious doping and trap introducing effects. Long time pumping in a high vacuum and 500 K annealing show negligible effects on removing the water adsorption on the devices. Current annealing at high source-drain bias is found to be able to remove the water adsorption and set the FETs to their initial states. The mechanism is proposed to be through the hot carriers at high bias.

Aptamers are an attractive molecular medicine that offers high target specificity. Nucleic acid-based aptamers, however, are prone to nuclease degradation and rapid renal excretion that require blood circulatory half-life extension enabling technologies. The long circulatory half-life, predominately facilitated by engagement with the cellular recycling neonatal Fc receptor (FcRn), and ligand transport properties of albumin promote it as an attractive candidate to improve the pharmacokinetic profile of aptamers. This study investigates the effect of Cys34 site-selective covalent attachment of a factor IXa anticoagulant aptamer on aptamer functionality and human FcRn (hFcRn) engagement using recombinant human albumin (rHA) of either a wild type (WT) or an engineered human FcRn high binding variant (HB). Albumin-aptamer conjugates, connected covalently through a heterobifunctional succinimidyl 4-(N-maleimidomethyl)cyclohexane-1-carboxylate linker, were successfully prepared and purified by high performance liquid chromatography as confirmed by gel electrophoresis band-shift analysis and matrix-assisted laser desorption/ionization time of flight. Minimal reduction (∼25%) in activity of WT-linked aptamer to that of aptamer alone was found using an anticoagulant activity assay measuring temporal levels of activated partial thrombin. Covalent albumin-aptamer conjugation, however, substantially compromized binding to hFcRn, to 10% affinity of that of non-conjugated WT, determined by biolayer interferometry. Binding could be rescued by aptamer conjugation to recombinant albumin engineered for higher FcRn affinity (HB) that exhibited an 8-fold affinity compared to WT alone. This work describes a novel albumin-based aptamer delivery system whose hFcRn binding can be increased using a HB engineered albumin.

Photocatalytic oxidation of graphene with ZnO nanoparticles was found to create self-assembled graphene oxide/graphene (G/GO) photosensitive heterostructures, which can be used as memristors. Oxygen groups released during photodecomposition of water molecules on the nanoparticles under ultraviolet light, oxidized graphene, locally forming the G/GO heterojunctions with ultra-high density. The G/GO nanostructures have non-linear current–voltage characteristics and switch the resistance in the dark and under white light, providing four resistive states at room temperature. Photocatalytic oxidation of graphene with ZnO nanoparticles is proposed as an effective method for creating two-dimensional memristors with a photoresistive switching for ultra-high capacity non-volatile memory.

We report europium (Eu)-induced changes in the π-band of graphene (G) formed on the 6H-SiC(0001) surface by a combined study of photoemission measurements and density functional theory (DFT) calculations. Our photoemission data reveal that Eu intercalates upon annealing at 120 °C into the region between the graphene and the buffer layer (BL) to form a G/Eu/BL system, where a band gap of 0.29 eV opens at room temperature. This band gap is found to increase further to 0.48 eV upon cooling down to 60 K. Our DFT calculations suggest that the increased band gap originates from the enhanced hybridization of the graphene π-band with the Eu 4f band due to the increased magnetic ordering upon cooling. These Eu atoms continue to intercalate further down below the BL to produce bilayer graphene (G/BL/Eu) upon annealing at 300 °C. The π-band stemming from the BL then exhibits another band gap of 0.37 eV, which appears to be due to the strong hybridization between the π-band of the BL and the Eu 4f band. The Eu-intercalated graphene thus illustrates an example of versatile band gaps formed under different thermal treatments, which may play a critical role for future applications in graphene-based electronics.

We report flexible resistive random access memory (ReRAM) arrays fabricated by using NiO_x/GaN microdisk arrays on graphene films. The ReRAM device was created from discrete GaN microdisk arrays grown on graphene films produced by chemical vapor deposition, followed by deposition of NiO_x thin layers and Au metal contacts. The microdisk ReRAM arrays were transferred to flexible plastic substrates by a simple lift-off technique. The electrical and memory characteristics of the ReRAM devices were investigated under bending conditions. Resistive switching characteristics, including cumulative probability, endurance, and retention, were measured. After 1000 bending repetitions, no significant change in the device characteristics was observed. The flexible ReRAM devices, constructed by using only inorganic materials, operated reliably at temperatures as high as 180 °C.

III–V semiconductor nanowires are a platform for next-generation photovoltaics. An interesting research direction is to embed a nanowire array in a transparent polymer, either to act as a stand-alone flexible solar cell, or to be stacked on top of a conventional Si bottom cell to create a tandem structure. To optimize the tandem cell performance, high energy photons should be absorbed in the nanowires whereas low energy photons should be transmitted to and absorbed in the Si cell. Here, through optical measurements on 1.95 eV bandgap GaInP nanowire arrays embedded in a polymer membrane, we identify two mechanisms that could be detrimental for the performance of the tandem cell. First, the Au particles used in the nanowire synthesis can absorb >50% of the low-energy photons, leading to a <40% transmittance, even though the Au particles cover <15% of the surface area. The removal of the Au particles can recover the transmission of low energy photons to >80%. Second, after the removal of the Au particles, a 40% reflectance peak shows up due to resonant back-scattering of light from in-plane waveguide modes. To avoid the excitation of these optical modes in the nanowire array, we propose to limit the pitch of the nanowire array.

InGaAs nanowires is one of the promising material systems of replacing silicon in future CMOS transistors, due to its high electron mobility in combination with the excellent electrostatic control from the tri-gate geometry. In this article, we report on gated Hall measurements on single and multiple In_0.85Ga_0.15As nanowires, selectively grown in a Hall bridge geometry with nanowire widths down to 50 nm and thicknesses of 10 nm. The gated nanowires can be used as junctionless transistors, which allows for a simplified device processing as no regrowth of contact layer or ion implantation is needed, which is particularly beneficial as transistor dimensions are scaled down. The analysis shows that the InGaAs layer has a carrier concentration of above 10¹⁹ cm⁻³, with a Hall carrier mobility of around 1000 cm² V⁻¹ s⁻¹. The gated Hall measurements reveal an increased carrier concentration as a function of applied gate voltage, with an increasing mobility for narrow nanowires but no significant effect on larger nanowires.

In this work, bimodal Cu nano-inks composed of two different sizes of Cu nanoparticles (NPs) (40 and 100 nm in diameter) were successfully sintered with a multi-pulse flashlight sintering technique. Bimodal Cu nano-inks were fabricated and printed with various mixing ratios and subsequently sintered by a flash light sintering method. The effects of the flashlight sintering conditions, including irradiation energy and pulse number, were investigated to optimize the sintering conditions. A detailed mechanism of the sintering of bimodal Cu nano-ink was also studied via real-time resistance measurement during the sintering process. The sintered Cu nano-ink films were characterized using x-ray photoelectron spectroscopy and scanning electron microscopy. From these results, it was found that the optimal ratio of 40–100 nm NPs was found to be 25:75 wt%, and the optimal multi-pulse flash light sintering condition (irradiation energy: 6 J cm⁻², and pulse duration: 1 ms, off-time: 4 ms, and pulse number: 5) was found. The optimally sintered Cu nano-ink film exhibited the lowest resistivity of 5.68 μΩ cm and 5B adhesion level.

We present the enhanced photoluminescence (PL) of a corrugated Al₂O₃ film enabled by colloidal CdSe quantum dots. The colloidal CdSe quantum dots are fabricated directly on a corrugated Al₂O₃ substrate using an electrochemical deposition (ECD) method in a microfluidic system. The photoluminescence is excited by using a 150 nm diameter ultraviolet laser spot of a scanning near-field optical microscope. Owing to the electron transfer from the conduction band of the CdSe quantum dots to that of Al₂O₃, the enhanced photoluminescence effect is observed, which results from the increase in the recombination rate of electrons and holes on the Al₂O₃ surface and the reduction in the fluorescence of the CdSe quantum dots. A periodically-fluctuating fluorescent spectrum was exhibited because of the periodical wire-like corrugated Al₂O₃ surface serving as an optical grating. The spectral topographic map around the fluorescence peak from the Al₂O₃ areas covered with CdSe quantum dots was unique and attributed to the uniform deposition of CdSe QDs on the corrugated Al₂O₃ surface. We believe that the microfluidic ECD system and the surface enhanced fluorescence method described in this paper have potential applications in forming uniform optoelectronic films of colloidal quantum dots with controllable QD spacing and in boosting the fluorescent efficiency of weak PL devices.

One of the most explored single quantum emitters for the development of nanoscale fluorescence lifetime imaging is the nitrogen-vacancy (NV) color center in diamond. An NV center does not experience fluorescence bleaching or blinking at room temperature. Furthermore, its optical properties are preserved when embedded into nanodiamond hosts. This paper focuses on the modeling of the local density of states (LDOS) in a plasmonic nanofocusing structure with an NV center acting as local illumination sources. Numerical calculations of the LDOS near such a nanostructure were done with a classical electric dipole radiation placed inside a diamond sphere as well as near-field optical fluorescence lifetime imaging of the structure. We found that Purcell factors higher than ten can be reached with diamond nanospheres of radius less than 5 nm and at a distance of less than 20 nm from the surface of the structure. Although the spatial resolution of the experiment is limited by the size of the nanodiamond, our work supports the analysis and interpretation of a single NV color center in a nanodiamond as a probe for scanning near-field optical microscopy.

The work presented in this paper concerns the synthesis of silicon (Si) 2D and 3D nanostructures using the delayed effect, caused by implanted Ga ions, on the dissolution of Si in aqueous solutions of tetramethylammonium hydroxide (TMAH). The crystalline silicon substrates (100) are first cleaned and then hydrogenated by immersion in an aqueous solution of hydrofluoric acid. The ion implantation is then carried out by a focused ion beam by varying the dose and the exposure time. Chemical etching in aqueous solutions of TMAH at 80 °C leads to the selective dissolution of the Si planes not exposed to the ions. The preliminary results obtained in the laboratory made it possible to optimize the experimental conditions for the synthesis of 2D and 3D nanoobjects of controlled shape and size. Analysis by transmission electron microscopy and energy dispersive x-ray showed the amorphous nature of the nanostructures obtained and the presence of 5%–20% Ga in these nanoobjects. The first experiments of recrystallization by rapid thermal annealing allowed to reconstitute the crystal structure of these nanoobjects.

We successfully prepared face-centred cubic nanoalloys in systems of Au–Ir, Au–Rh and Au–Ir–Rh, with large bulk miscibility gaps, in one-run reactions under thermal decomposition of specially synthesised single-source precursors, namely, [AuEn₂][Ir(NO₂)₆], [AuEn₂][Ir(NO₂)₆]_х[Rh(NO₂)₆]_1−х and [AuEn₂][Rh(NO₂)₆]. The precursors employed contain all desired metals 'mixed' at the atomic level, thus providing significant advantages for obtaining alloys. The observations using high-resolution transmission electron microscopy show that the nanoalloy structures are composed of well-dispersed aggregates of crystalline domains with a mean size of 5 ± 3 nm. Еnergy dispersive x-ray spectroscopy and x-ray powder diffraction (XRD) measurements confirm the formation of AuIr, AuRh, AuIr_0.75Rh_0.25, AuIr_0.50Rh_0.50 and AuIr_0.25Rh_0.75 metastable solid solutions. In situ high-temperature synchrotron XRD (HTXRD) was used to study the formation mechanism of nanoalloys. The observed transformations are described by the 'conversion chemistry' mechanism characterised by the primary development of particles comprising atoms of only one type, followed by a chemical reaction resulting in the final formation of a nanoalloy. The obtained metastable nanoalloys exhibit essential thermal stability. Exposure to 180 °C for 30 h does not cause any dealloying process.

Nanoimprint lithography (NIL) is one of the most prominent bottom-up techniques for duplicating nanostructures with a high throughput. However, fabrication of starting master mold commonly requires expensive equipment of top-down techniques, or additional steps to transfer the fabricated patterns from bottom-up methods. Here we demonstrate that a SiO₂ nanostructure manufactured from a self-assembled block copolymer, polystyrene-b-polydimethylsiloxane (PS-b-PDMS), directly serves as a master mold for NIL without further modification. A hexagonally aligned pattern over the entire substrate is established using a simple technique; solvent annealing and etching. Etching also plays an important role in endowing fluorine on the surface of SiO₂, thus promoting smooth demolding upon imprinting. The obtained pattern of the SiO₂ nanostructure is transferred to a polymer surface using UV nanoimprint. Identical patterns of the SiO₂ nanostructure are elaborately reproduced on Ni and Cu nanodot arrays via electroplating on the polymer transcript, which was verified by morphological observations. The uniformity of the replicated Ni nanodot array is evaluated using spectroscopic ellipsometry. The measured optical response of the Ni nanodot is validated by electromagnetically simulated results, indicating that the pattern transfer is not limited to a small local area. In addition, the durability of the SiO₂ mold pattern is corroborated after the imprinting process, thus guaranteeing the reusability of the fabricated nanostructure as a master mold. The proposed approach does not require any high-end lithographic techniques; this may result in significant cost and time reductions in future nanofabrication.

Organic field-effect transistors (OFETs) have been developed over the past few decades due to their potential applications in future electronics such as wearable and foldable electronics. As the electrical performance of OFETs has improved, patterning organic semiconducting crystals has become a key issue for their commercialization. However, conventional soft lithographic techniques have required the use of expensive processes to fabricate high-resolution master molds. In this study, we demonstrated a cost-effective method to prepare nanopatterned master molds for the fabrication of high-performance nanowire OFETs. We repurposed commercially available compact discs (CDs) as master molds because they already have linear nanopatterns on their surface. Flexible nanopatterned templates were replicated from the CDs using UV-imprint lithography. Subsequently, 6,13-bis-(triisopropylsilylethynyl) pentacene nanowires (NWs) were grown from the templates using a capillary force-assisted lithographic technique. The NW-based OFETs showed a high average field-effect mobility of 2.04 cm² V⁻¹ s⁻¹. This result was attributed to the high crystallinity of the NWs and to their crystal orientation favorable for charge transport.

Solution-processed polycrystalline perovskite films contribute critically to the high photovoltaic performance of perovskite-based solar cells (PSCs). The inevitable electronic trap states at grain boundaries and intrinsic defects such as metallic lead (Pb⁰) and halide vacancies in perovskite films cause serious carrier recombination loss. Furthermore, the film can easily decompose into PbI₂ in a moist atmosphere. Here, we introduce a simple strategy, through a small increase in methylammonium iodide (CH₃NH₃I, MAI), molar proportion (5%), for perovskite fabrication in ambient air with ∼50% relative humidity. Analysis of the morphology and crystallography demonstrates that excess MAI significantly promotes grain growth without decomposition. X-ray photoemission spectroscopy shows that no metallic Pb⁰ exists in the perovskite film and the I/Pb ratio is improved. A time-resolved photoluminescence measurement indicates efficient suppression of non-radiative recombination in the perovskite layer. As a result, the device yields improved power conversion efficiency from 14.06% to 18.26% with reduced hysteresis and higher stability under AM1.5G illumination (100 mW cm⁻²). This work strongly provides a feasible and low-cost way to develop highly efficient PSCs in ambient air.

A class of highly sensitive chemiresistive sensors is developed for methanol (MeOH) vapor detection in ambient atmosphere by introducing conductive nanofillers like carbon black, multi-wall carbon nanotubes, and reduced graphene oxide into sulfonated poly(etherimide) (PEI)/liquid crystal polymer (LCP) composite (sPEI-LCP). Polar composites are prepared by a sulfonation process for instantaneous enhancement in adsorption capability of the sensing films to the target analyte (MeOH). Sensing properties exhibit that polymer composite-based fabricated sensors are efficient for the detection of different concentration of methanol vapor from 300–1200 parts-per-million (ppm) at room temperature. The incorporation of nanofiller induces the dramatic change in sensing behavior of base composite film (sPEI-LCP). Thus, less mass fraction of nanofillers (i.e. 2 wt%) influences the nonlinear sensing behavior for the entire range of methanol vapor. The simple method and low fabrication cost of the prepared sensor are compelling reasons that methanol vapor sensor is suitable for environmental monitoring. 

To balance the stability and the particle size of polymeric micelles, star-shaped copolymers Hx-yne-N₃-PEG containing both alkynyl and azido groups were synthesized from hyperbranched 2,2-bismethylolpropionic acid polyester (H20 with 16 hydroxyl, H30 with 32 hydroxyl, H40 with 64 hydroxyl) to develop interlayer-crosslinked micelles by click chemistry. The results of dynamic light scattering indicate that the crosslinking could enhance the stability of polymeric micelles. The crosslinked micelles are regular nanosized (approximately 20 nm) spheres observed by a transmission electron microscope. The crosslinked micelles have better drug loading capacity and more sustained drug release behavior than the un-crosslinked micelles.

The growth of Fe nanostructures on the stoichiometric MoO₂/Mo(110) and oxygen-rich MoO_2+x/Mo(110) surfaces has been studied using low-temperature scanning tunnelling microscopy (STM) and density functional theory calculations. STM results indicate that at low coverage Fe nucleates on the MoO₂/Mo(110) surface, forming small, well-ordered nanoclusters of uniform size, each consisting of five Fe atoms. These five-atom clusters can agglomerate into larger nanostructures reflecting the substrate geometry, but they retain their individual character within the structure. Linear Fe nanocluster arrays are formed on the MoO₂/Mo(110) surface at room temperature when the surface coverage is greater than 0.6 monolayers. These nanocluster arrays follow the direction of the oxide rows of the strained MoO₂/Mo(110) surface. Slightly altering the preparation procedure of MoO₂/Mo(110) leads to the presence of oxygen adatoms on this surface. Fe deposition onto the oxygen-rich MoO_2+x/Mo(110) surface results in elongated nanostructures that reach up to 24 nm in length. These nanolines have a zigzag shape and are likely composed of partially oxidised Fe formed upon reaction with the oxygen-rich surface.

The detection and removal of nitroaromatic compounds is an important issue for environmental protection. In this study, a hybrid of molybdenum disulfide (MoS₂) and graphene (GR) was first synthesized using a facile hydrothermal method. Au and Ag nanoparticles were then deposited onto the surface of the MoS₂/GR hybrid with sodium citrate as the stabilizer and reductant. Compared to using pure MoS₂ as the support, the obtained Au (Ag)-MoS₂/GR composites showed improved activity for electrochemical detection and chemical reduction of 4-nitrophenol. The activity enhancement appears to be due to the addition of GR, which could improve the conductivity as well as provide more active sites. The successful synthesis of Au (Ag)-MoS₂/GR composites could provide new multi-function catalysts for environmental protection.

This work reports the structural and vibrational properties of nanocrystals of corundum-type In₂O₃ (rh-In₂O₃) at high pressures by using angle-dispersive x-ray diffraction and Raman scattering measurements up to 30 GPa. The equation of state and the pressure dependence of the Raman-active modes of the corundum phase in nanocrystals are in good agreement with previous studies on bulk material and theoretical simulations on bulk rh-In₂O₃. Nanocrystalline rh-In₂O₃ showed stability under compression at least up to 20 GPa, unlike bulk rh-In₂O₃ which gradually transforms to the orthorhombic Pbca (Rh₂O₃-III-type) structure above 12–14 GPa. The different stability range found in nanocrystalline and bulk corundum-type In₂O₃ is discussed.

Metal nanoparticles (NPs), in particular gold NPs, are often used in the fabrication process of semiconductor nanowires. Besides being able to induce the 1D crystallization of new material, it is highly beneficial if the NPs can be used to dictate the position and diameter of the final nanowire structure. To achieve well-defined NP arrays of varying diameter and pitch distances for nanowire growth, it is necessary to understand and control the effect that a pre-growth annealing process may have on the pre-defined NP arrays. Recently, it has been demonstrated that silver (Ag) may be an alternative to using gold (Au) NPs as seed for particle-seeded nanowire fabrication. This work brings light onto the effect of annealing of Au, Ag and Au–Ag alloy metal NP arrays in two commonly used epitaxial systems, the molecular beam epitaxy (MBE) and the metalorganic vapor phase epitaxy (MOVPE). The metal NP arrays are fabricated with the aid of electron beam lithography on GaAs 100 and 111B wafers and the evolution of the NPs with respect to shape, size and position on the surfaces is studied after annealing using scanning electron microscopy. We find that while the Au NP arrays are found to be stable when annealed up to 600 °C in a MOVPE system, a diameter and pitch dependent splitting of the particles is seen for annealing in a MBE system. The Ag NP arrays are found to be less stable, with smaller diameters (≤50 nm) dissolving during the annealing process in both epitaxial systems. In general, the mobility of the NPs is observed to differ between the two the GaAs 100 and 111B surfaces. Finally, our observations on the effect of annealing on Au–Ag alloy NP arrays suggest that these NP can withstand necessary annealing conditions for a complete de-oxidation of GaAs surfaces in both MOVPE and MBE.