Nanoscale core-shell structure and recrystallization of swift heavy ion tracks in SrTiO3.

It is widely accepted that the interaction of swift heavy ions with many complex oxides is predominantly governed by the electronic energy loss that gives rise to nanoscale amorphous ion tracks along the penetration direction. The question of how electronic excitation and electron-phonon coupling affect the atomic system through defect production, recrystallization, and strain effects has not yet been fully clarified. To advance the knowledge of the atomic structure of ion tracks, we irradiated single crystalline SrTiO3 with 629 MeV Xe ions and performed comprehensive electron microscopy investigations complemented by molecular dynamics simulations. This study shows discontinuous ion-track formation along the ion penetration path, comprising an amorphous core and a surrounding few monolayer thick shell of strained/defective crystalline SrTiO3. Using machine-learning-aided analysis of atomic-scale images, we demonstrate the presence of 4-8% strain in the disordered region interfacing with the amorphous core in the initially formed ion tracks. Under constant exposure of the electron beam during imaging, the amorphous part of the ion tracks readily recrystallizes radially inwards from the crystalline-amorphous interface under the constant electron-beam irradiation during the imaging. Cation strain in the amorphous region is observed to be significantly recovered, while the oxygen sublattice remains strained even under the electron irradiation due to the present oxygen vacancies. The molecular dynamics simulations support this observation and suggest that local transient heating and annealing facilitate recrystallization process of the amorphous phase and drive Sr and Ti sublattices to rearrange. In contrast, the annealing of O atoms is difficult, thus leaving a remnant of oxygen vacancies and strain even after recrystallization. This work provides insights for creating and transforming novel interfaces and nanostructures for future functional applications.

Experimental evidence of a size-dependent sign change of the Seebeck coefficient of Bi nanowire arrays.

The electrical transport in bismuth nanowires is strongly influenced by both sample geometry and crystallinity. Compared to bulk bismuth, the electrical transport in nanowires is dominated by size effects and influenced by surface states, which gain increasing relevance with increasing surface-to-volume ratios, i.e. with decreasing wire diameter. Bismuth nanowires with tailored diameter and crystallinity constitute, therefore, excellent model systems, allowing to study the interplay of the different transport phenomena. Here, we present temperature-dependent Seebeck coefficient and relative electrical resistance measurements of parallel bismuth nanowire arrays with diameters between 40 and 400 nm synthesized by pulsed electroplating in polymer templates. Both electrical resistance and Seebeck coefficient exhibit a non-monotonic temperature dependence, with the sign of the Seebeck coefficient changing from negative to positive with decreasing temperature. The observed behavior is size-dependent and is attributed to limitations of the mean free path of the charge carriers within the nanowires. The observed size-dependent Seebeck coefficient and in particular the size-dependent sign change opens a promising avenue for single-material thermocouples with p- and n-legs made from nanowires with different diameters.

Three-dimensional free-standing gold nanowire networks as a platform for catalytic applications.

We report the catalytic performance of networks of highly interconnected Au nanowires with diameters tailored between 80 and 170 nm. The networks were synthesized by electrodeposition in etched ion-track polymer templates, and the synthesis conditions were developed for optimal wire crystallinity and network homogeneity. The nanowire networks were self-supporting and could be easily handled as electrodes in electrochemical cells or other devices. The electrochemically active surface area of the networks increased systematically with increasing the wire diameter. They showed a very stable performance during 200 CV cycles of methanol oxidation reactions, with the peak current density reaching up to 200 times higher than that of a flat reference electrode, with only a 5% drop in the peak current density. The Au nanowire networks proved to be excellent model systems for investigation of the performance of porous catalysts and very promising nanosystems for application in direct alcohol fuel cell catalysts.

Electrochemically addressed FET-like nanofluidic channels with dynamic ion-transport regimes.

Nanofluidic channels in which the ionic transport can be modulated by the application of an external voltage to the nanochannel walls have been described as nanofluidic field effect transistors (nFETs) because of their analogy with electrolyte-gated field effect transistors. The creation of nFETs is attracting increasing attention due to the possibility of controlling ion transport by using an external voltage as a non-invasive stimulus. In this work, we show that it is possible to extend the actuation range of nFETs by using the supporting electrolyte as a "chemical effector". For this aim, a gold-coated poly(ethylene terephthalate) (PET) membrane was modified with electroactive poly-o-aminophenol. By exploiting the interaction between the electroactive poly-o-aminophenol and the ions in the electrolyte solution, the magnitude and surface charge of the nanochannels were fine-tuned. In this way, by setting the electrolyte nature it has been possible to set different ion transport regimes, i.e.: cation-selective or anion-selective ion transport, whereas the rectification efficiency of the ionic transport was controlled by the gate voltage applied to the electroactive polymer layer. Remarkably, under both regimes, the platform displays a reversible and rapid response. We believe that this strategy to preset the actuation range of nFETs by using the supporting electrolyte as a chemical effector can be extended to other devices, thus offering new opportunities for the development of stimulus-responsive solid-state nanochannels.

Thinning of Poly(methyl methacrylate) and Poly(vinyl chloride) Thin Films Induced by High-Energy Ions of Different Stopping Powers.

Ion bombardment is an important tool of materials processing, but usually leads to erosion of the surface and significant thickness reductions when thin layers are used. The growing use of polymer thin films in a variety of applications, from coatings and membranes to biomedical and electronic devices, calls for a deeper understanding of the thinning process induced by energetic ions espe-cially for very thin films. Here, thinning and surface morphology changes induced by high-energy ion bombardment in PMMA and PVC thin films were investigated, focusing on the role of the initial thickness of the films and the stopping power of the ions. We used thin films with initial thicknesses varying from 13 to 800 nm, and light and heavy ions as projectiles in the energy range of 2-2000 MeV, where the electronic stopping dominates. Thickness reductions as a function of fluence were monitored and thinning cross sections were extracted from curves. A supralinear scaling between the thinning cross sections and the electronic stopping power of the beams was observed, with a much enhanced thinning efficiency for the swift heavy ions. The scaling with the stopping power dE/dx is almost independent of the initial thickness of the films. At intermediate and large fluences, changes in the physicochemical properties of the irradiated polymers may modulate and decelerate the thinning process of the remaining film. The importance of this secondary process depends on the stopping power and the balance between erosion and the chemical transformations induced by the beam. We also observe a trend for the thinning efficiency to become larger in very thin films. Depending on the type of beam and polymer, this effect is more or less pronounced. PMMA films irradiated with 2 MeV H+ show the most systematic correlation between initial thickness and thinning cross sections, while in PVC films the initial thickness plays a minor role for all investigated beams.

Switchable Ion Current Saturation Regimes Enabled via Heterostructured Nanofluidic Devices Based on Metal-Organic Frameworks.

The use of track-etched membranes allows further fine-tuning of transport regimes and thus enables their use in (bio)sensing and energy-harvesting applications, among others. Recently, metal-organic frameworks (MOFs) have been combined with such membranes to further increase their potential. Herein, the creation of a single track-etched nanochannel modified with the UiO-66 MOF is proposed. By the interfacial growth method, UiO-66-confined synthesis fills the nanochannel completely and smoothly, yet its constructional porosity renders a heterostructure along the axial coordinate of the channel. The MOF heterostructure confers notorious changes in the transport regime of the nanofluidic device. In particular, the tortuosity provided by the micro- and mesostructure of UiO-66 added to its charged state leads to iontronic outputs characterized by an asymmetric ion current saturation for transmembrane voltages exceeding 0.3 V. Remarkably, this behavior can be easily and reversibly modulated by changing the pH of the media and it can also be maintained for a wide range of KCl concentrations. In addition, it is found that the modified-nanochannel functionality cannot be explained by considering just the intrinsic microporosity of UiO-66, but rather the constructional porosity that arises during the MOF growth process plays a central and dominant role.

Triazol-Methanaminium-Pillar[5]arene-Functionalized Single Nanochannel for Quantitative Analysis of Pyrophosphate in Water.

Inorganic pyrophosphate (PPi) is an important biological functional anion and plays crucial roles in life science, environmental science, medicine, and chemical process. Quantification of PPi in water has far-reaching significance for life exploration, disease diagnosis, and water pollution control. The label-free quantitative detection of PPi anions with a nanofluidic sensing device based on a conical single nanochannel is demonstrated. The channel surface is functionalized with a synthetic PPi receptor, triazol-methanaminium-functionalized pillar[5]arene (TAMAP5), using carbodiimide coupling chemistry. Due to the specific binding between TAMAP5 and PPi, the functionalized nanochannel can discriminate PPi from other inorganic anions with high selectivity through ionic current recording, even in the presence of various interfering anions. The current response exhibits a linear correlation with PPi concentration in the range from 1 × 10-7 to 1 × 10-4 M with a limit of detection of 6.8 × 10-7 M. A spike-and-recovery analysis of PPi in East Lake water samples indicates that the proposed nanofluidic sensor has the ability to quantitate micromolar concentrations of PPi in environmental water samples.

Structural and Electrical Response of Emerging Memories Exposed to Heavy Ion Radiation.

Hafnium oxide- and GeSbTe-based functional layers are promising candidates in material systems for emerging memory technologies. They are also discussed as contenders for radiation-harsh environment applications. Testing the resilience against ion radiation is of high importance to identify materials that are feasible for future applications of emerging memory technologies like oxide-based, ferroelectric, and phase-change random-access memory. Induced changes of the crystalline and microscopic structure have to be considered as they are directly related to the memory states and failure mechanisms of the emerging memory technologies. Therefore, we present heavy ion irradiation-induced effects in emerging memories based on different memory materials, in particular, HfO2-, HfZrO2-, as well as GeSbTe-based thin films. This study reveals that the initial crystallinity, composition, and microstructure of the memory materials have a fundamental influence on their interaction with Au swift heavy ions. With this, we provide a test protocol for irradiation experiments of hafnium oxide- and GeSbTe-based emerging memories, combining structural investigations by X-ray diffraction on a macroscopic, scanning transmission electron microscopy on a microscopic scale, and electrical characterization of real devices. Such fundamental studies can be also of importance for future applications, considering the transition of digital to analog memories with a multitude of resistance states.

Highly sensitive acetylcholine biosensing via chemical amplification of enzymatic processes in nanochannels.

Acetylcholinesterase-modified nanochannels are proposed as reliable and reproducible nanofluidic sensors for highly sensitive detection of acetylcholine. The operation mechanism relies on the use of weak polyelectrolytes as "chemical amplifiers" that adjust/reconfigure the nanochannel surface charge in the presence of local pH changes induced by the enzymatic reaction. Experimental results show that the presence of acetylcholine can be transduced into measurable ionic signals with a low limit of detection.

Nanofluidic osmotic power generators - advanced nanoporous membranes and nanochannels for blue energy harvesting.

The increase of energy demand added to the concern for environmental pollution linked to energy generation based on the combustion of fossil fuels has motivated the study and development of new sustainable ways for energy harvesting. Among the different alternatives, the opportunity to generate energy by exploiting the osmotic pressure difference between water sources of different salinities has attracted considerable attention. It is well-known that this objective can be accomplished by employing ion-selective dense membranes. However, so far, the current state of this technology has shown limited performance which hinders its real application. In this context, advanced nanostructured membranes (nanoporous membranes) with high ion flux and selectivity enabling the enhancement of the output power are perceived as a promising strategy to overcome the existing barriers in this technology. While the utilization of nanoporous membranes for osmotic power generation is a relatively new field and therefore, its application for large-scale production is still uncertain, there have been major developments at the laboratory scale in recent years that demonstrate its huge potential. In this review, we introduce a comprehensive analysis of the main fundamental concepts behind osmotic energy generation and how the utilization of nanoporous membranes with tailored ion transport can be a key to the development of high-efficiency blue energy harvesting systems. Also, the document discusses experimental issues related to the different ways to fabricate this new generation of membranes and the different experimental set-ups for the energy-conversion measurements. We highlight the importance of optimizing the experimental variables through the detailed analysis of the influence on the energy capability of geometrical features related to the nanoporous membranes, surface charge density, concentration gradient, temperature, building block integration, and others. Finally, we summarize some representative studies in up-scaled membranes and discuss the main challenges and perspectives of this emerging field.

Direct detection of human adenovirus or SARS-CoV-2 with ability to inform infectivity using DNA aptamer-nanopore sensors.

Viral infections are a major global health issue, but no current method allows rapid, direct, and ultrasensitive quantification of intact viruses with the ability to inform infectivity, causing misdiagnoses and spread of the viruses. Here, we report a method for direct detection and differentiation of infectious from noninfectious human adenovirus and SARS-CoV-2, as well as from other virus types, without any sample pretreatment. DNA aptamers are selected from a DNA library to bind intact infectious, but not noninfectious, virus and then incorporated into a solid-state nanopore, which allows strong confinement of the virus to enhance sensitivity down to 1 pfu/ml for human adenovirus and 1 × 104 copies/ml for SARS-CoV-2. Applications of the aptamer-nanopore sensors in different types of water samples, saliva, and serum are demonstrated for both enveloped and nonenveloped viruses, making the sensor generally applicable for detecting these and other emerging viruses of environmental and public health concern.

Conical Nanotubes Synthesized by Atomic Layer Deposition of Al2O3, TiO2, and SiO2 in Etched Ion-Track Nanochannels.

Etched ion-track polycarbonate membranes with conical nanochannels of aspect ratios of ~3000 are coated with Al2O3, TiO2, and SiO2 thin films of thicknesses between 10 and 20 nm by atomic layer deposition (ALD). By combining ion-track technology and ALD, the fabrication of two kinds of functional structures with customized surfaces is presented: (i) arrays of free-standing conical nanotubes with controlled geometry and wall thickness, interesting for, e.g., drug delivery and surface wettability regulation, and (ii) single nanochannel membranes with inorganic surfaces and adjustable isoelectric points for nanofluidic applications.

Borate-driven ionic rectifiers based on sugar-bearing single nanochannels.

Recently, much scientific effort has been centered on the control of the ionic transport properties of solid state nanochannels and the rational design and integration of chemical systems to induce changes in the ionic transport by means of interactions with selected target molecules. Here, we report the fabrication of a novel nanofluidic device based on solid-state nanochannels, which combines silane chemistry with both track-etched and atomic layer deposition (ALD) technologies. Nanodevice construction involves the coating of bullet-shaped single-pore nanochannels with silica (SiO2) by ALD and subsequent surface modification by reaction between silanol groups exposed on pore walls and N-(3-triethoxysilylpropyl)-gluconamide, in order to create a gluconamide-decorated nanochannel surface. The formation of a boroester derivative resulting from the selective reaction of borate with the appended saccharides leads to important changes in the surface charge density and, concomitantly, in the iontronic properties of the nanochannel. Furthermore, we propose a binding model to rationalize the specific interaction saccharide-borate in the surface. Besides, this unique nanodevice exhibits a highly selective and reversible response towards borate/fructose exposure. On the basis of the surface charge variation resulting from borate binding, the nanochannel can reversibly switch between "ON" and "OFF" states in the presence of borate and fructose, respectively. In addition, this work describes the first report of the functionalization of PET/SiO2 nanochannels by the ALD technique. We believe that this work provides a promising framework for the development of new nanochannel-based platforms suitable for multiple applications, such as water quality monitoring or directed molecular transport and separation.

Ion track etching of polycarbonate membranes monitored by in situ small angle X-ray scattering.

In situ small angle X-ray scattering (SAXS) measurements of ion track etching in polycarbonate foils are used to directly monitor the selective dissolution of ion tracks with high precision, including the early stages of etching. Detailed information about the track etching kinetics and size, shape, and size distribution of an ensemble of nanopores is obtained. Time resolved measurements as a function of temperature and etchant concentration show that the pore radius increases almost linearly with time for all conditions and the etching process can be described by an Arrhenius law. The radial etching shows a power law dependency on the etchant concentration. An increase in the etch rate with increasing temperature or concentration of the etchant reduces the penetration of the etchant into the polymer but does not affect the pore size distribution. The in situ measurements provide an estimate for the track etch rate, which is found to be approximately three orders of magnitude higher than the radial etch rate. The measurement methodology enables new experiments studying membrane fabrication and performance in liquid environments.

Etched ion-track membranes as tailored separators in Li-S batteries.

Lithium-sulfur (Li-S) batteries are considered a promising next generation alternative to lithium-ion batteries for energy storage systems due to its high energy density. However, several challenges, such as the polysulfide redox shuttle causing self-discharge of the battery, remain unresolved. In this paper, we explore the use of polymer etched ion-track membranes as separators in Li-S batteries to mitigate the redox shuttle effect. Compared to commercial separators, their unique advantages lie in their very narrow pore size distribution, and the possibility to tailor and optimize the density, geometry, and diameter of the nanopores in an independent manner. Various polyethylene terephthalate membranes with diameters between 22 and 198 nm and different porosities were successfully integrated into Li-S coin cells. The reported coulombic efficiency of up to 97% with minor reduction in capacity opens a pathway to potentially address the polysulfide redox shuttle in Li-S batteries using tailored membranes.

Efficient Chiral Nanosenor Based on Tip-Modified Nanochannels.

Enantiomers of various drug molecules have a specific effect on living organisms. Accordingly, developing a sample method for the efficient and rapid recognition of chiral drug enantiomers is of great industrial value and physiological significance. Here, inspired by the structure of ion channels in living organisms, we developed a chiral nanosensor based on an artificial tip-modified nanochannel system that allows efficient selective recognition of chiral drugs. In this system, l-alanine-pillar[5]arenes as selective receptors were introduced on the tip side of conical nanochannels to form an enantioselective "gate". The selective coefficient of our system toward R-propranolol is 4.96, which is higher than the traditional fully modified nanochannels in this work.

Selective transmembrane transport of Aß protein regulated by tryptophan enantiomers.

Tryptophan enantiomers (d/l-Trp) were introduced into artificial nanochannels to regulate the chiral selective transport of Aß proteins. The l-Trp channel performs effectively selectivity for the transport of Aß protein, which would provide a new perspective for the pathological studies of Alzheimer's disease.

High-sensitivity detection of dopamine by biomimetic nanofluidic diodes derivatized with poly(3-aminobenzylamine).

During the last few years, much scientific effort has been devoted to the control of ionic transport properties of solid state nanochannels and the rational integration of chemical systems to induce changes in the ionic transport by interaction with selected target molecules for (bio)sensing purposes. In this work, we present the construction and functional evaluation of a highly sensitive dopamine-responsive iontronic device by functionalization of bullet-shaped track-etched single nanochannels in PET membranes with poly(3-aminobenzylamine) (PABA). The variety of basic groups in this amino-appended polyaniline derivative allows programming of the ion selectivity of the channel by setting the pH conditions. On the other hand, the amino-pendant groups of PABA become suitable binding sites for the selective chemical reaction with dopamine, leading to a change in the nanochannel surface charge. Thus, the exposure of the PABA-modified nanochannel to dopamine solutions selectively produces changes in the iontronic response. By rationally selecting the conditions for both the dopamine binding step and the iontronic reading, we obtained a correlation between the rectification efficiency and dopamine concentration down to the nanomolar range, which was also successfully interpreted in terms of a simple binding model.

Polyaniline for Improved Blue Energy Harvesting: Highly Rectifying Nanofluidic Diodes Operating in Hypersaline Conditions via One-Step Functionalization.

Solid-state nanochannels have attracted substantial attention of the scientific community due to their remarkable control of ionic transport and the feasibility to regulate the iontronic output by different stimuli. Most of the developed nanodevices are subjected to complex modification methods or show functional responsiveness only in moderate-ionic-strength solutions. Within this project, we present a nanofluidic device with enhanced ionic current rectification properties attained by a simple one-step functionalization of single bullet-shaped polyethylene terephthalate (PET) nanochannels with polyaniline (PANI) that can work in high-ionic-strength solutions. The integration of PANI also introduces a broad pH sensitivity, which makes it possible to modulate the ionic transport behavior between anion-selective and cation-selective regimes depending on the pH range. Since PANI is an electrochemically active polymer, ionic transport also becomes dependent on the presence of redox stimuli in solution. We demonstrate that PANI-functionalized single-nanochannel membranes function as an efficient salinity gradient-based energy conversion device even in acidic concentrated salt solutions, opening the door to applications under a variety of novel operating conditions.

Electrochemically addressable nanofluidic devices based on PET nanochannels modified with electropolymerized poly-o-aminophenol films.

Nanofluidic field-effect transistors (nFETs) have attracted attention from the scientific community due to their remarkable level of control over ionic transport. Particularly, the combination of nanofluidic systems and electroactive polymers has demonstrated to be an interesting approach to achieve an electrochemically addressable device. In this work, the development of nFETs based on the integration of electropolymerized poly-o-aminophenol (POAP) films into track-etched nanochannels is proposed. The electropolymerization of POAP on the tip side of Au-sputtered asymmetric PET nanochannels not only allowed having a programmable tip diameter but also offered a precise and very rapid control of ionic transport by switching an external bias voltage. Moreover, the system exhibited a reversible behaviour between non-selective and anion-selective states. We believe that this work provides new tools and concepts to design and build high-performance nanofluidic field-effect transistors working under electrochemically controlled conditions.