Charge Shielding-Oriented Design of Zinc-Based Nanoparticle Liquids for Controlled Nanofabrication.

Metal-containing nanoparticles possess nanoscale sizes, but the exploitation of their nanofeatures in nanofabrication processes remains challenging. Herein, we report the realization of a class of zinc-based nanoparticle liquids and their potential for applications in controlled nanofabrication. Utilizing the metal-core charge shielding strategy, we prepared nanoparticles that display glass-to-liquid transition behavior with glass transition temperature far below room temperature (down to -50.9 °C). Theoretical calculations suggest the outer surface of these unusual nanoparticles is almost neutral, thus leading to interparticle interactions weak enough to give them liquefaction characteristics. Such features endow them with extraordinarily high dispersibility and excellent film-forming capabilities. Twenty-two types of nanoparticles synthesized by this strategy have all shown good lithographic properties in the mid-ultraviolet, electron beam, or extreme ultraviolet light, and these nanoparticle liquids have achieved controlled top-down nanofabrication with predesigned 18 or 16 nm patterns. This proposed strategy is synthetically scalable and structurally extensible and is expected to inspire the design of entirely new forms of nanomaterials.

Catalyst support effects on hydrogen spillover.

Hydrogen spillover is the surface migration of activated hydrogen atoms from a metal catalyst particle, on which they are generated, onto the catalyst support. The phenomenon has been much studied and its occurrence on reducible supports such as titanium oxide is established, yet questions remain about whether hydrogen spillover can take place on nonreducible supports such as aluminium oxide. Here we use the enhanced precision of top-down nanofabrication to prepare controlled and precisely tunable model systems that allow us to quantify the efficiency and spatial extent of hydrogen spillover on both reducible and nonreducible supports. We place multiple pairs of iron oxide and platinum nanoparticles on titanium oxide and aluminium oxide supports, varying the distance between the pairs from zero to 45 nanometres with a precision of one nanometre. We then observe the extent of the reduction of the iron oxide particles by hydrogen atoms generated on the platinum using single-particle in situ X-ray absorption spectromicroscopy applied simultaneously to all particle pairs. The data, in conjunction with density functional theory calculations, reveal fast hydrogen spillover on titanium oxide that reduces remote iron oxide nanoparticles via coupled proton-electron transfer. In contrast, spillover on aluminium oxide is mediated by three-coordinated aluminium centres that also interact with water and that give rise to hydrogen mobility competing with hydrogen desorption; this results in hydrogen spillover about ten orders of magnitude slower than on titanium oxide and restricted to very short distances from the platinum particle. We anticipate that these observations will improve our understanding of hydrogen storage and catalytic reactions involving hydrogen, and that our approach to creating and probing model catalyst systems will provide opportunities for studying the origin of synergistic effects in supported catalysts that combine multiple functionalities.

Charge Configuration Memory Devices: Energy Efficiency and Switching Speed.

Current trends in data processing have given impetus for an intense search of new concepts of memory devices with emphasis on efficiency, speed, and scalability. A promising new approach to memory storage is based on resistance switching between charge-ordered domain states in the layered dichalcogenide 1T-TaS2. Here we investigate the energy efficiency scaling of such charge configuration memory (CCM) devices as a function of device size and data write time τW as well as other parameters that have bearing on efficient device operation. We find that switching energy efficiency scales approximately linearly with both quantities over multiple decades, departing from linearity only when τW approaches the ∼0.5 ps intrinsic switching limit. Compared to current state of the art memory devices, CCM devices are found to be much faster and significantly more energy efficient, demonstrated here with two-terminal switching using 2.2 fJ, 16 ps electrical pulses.

High-efficiency diffraction gratings for EUV and soft x-rays using spin-on-carbon underlayers.

We report on the fabrication and characterization of high-resolution gratings with high efficiency in the extreme ultraviolet (EUV) and soft x-ray ranges using spin-on-carbon (SOC) underlayers. We demonstrate the fabrication of diffraction gratings down to 20 nm half-pitch (HP) on Si3N4membranes with a bilayer of hydrogen silsesquioxane (HSQ) and spin-on-carbon and show their performance as a grating mask for extreme ultraviolet interference lithography (EUV-IL). High-resolution patterning of HSQ is possible only for thin films due to pattern collapse. The combination of this high-resolution resist with SOC circumvents this problem and enables the fabrication of high aspect ratio nanostructures. Rigorous coupled-wave analysis shows that the bilayer gratings exhibit higher diffraction efficiency than what is feasible with a grating made of HSQ. We also demonstrate a simple and accurate method to experimentally measure the diffraction efficiency of high-resolution gratings by measuring the relative ratio of the dose-to-clear curves of the photoresist. The measured diffraction efficiencies are in good agreement with the theoretically predicted values. Furthermore, we verify our calculations and measurements by printing line/space patterns in chemically amplified resists down to 10 nm HP with both HSQ and bilayer grating masks using EUV-IL. The improved diffraction efficiency of the bilayers is expected to have applications not only in gratings for interference lithography, but also in Fresnel zone plates and gratings for spectroscopy in the EUV and soft x-ray ranges.

Beam drift and partial probe coherence effects in EUV reflective-mode coherent diffractive imaging.

While the industrial implementation of extreme ultraviolet lithography for upcoming technology nodes is becoming ever more realistic, a number of challenges have yet to be overcome. Among them is the need for actinic mask inspection. We report on reflective-mode lensless imaging of a patterned multi-layer mask sample at extreme ultraviolet wavelength that provides a finely structured defect map of the sample under test. Here, we present the imaging results obtained using ptychography in reflection mode at 6° angle of incidence from the surface normal and 13.5 nm wavelength. Moreover, an extended version of the difference map algorithm is employed that substantially enhances the reconstruction quality by taking into account both long and short-term variations of the incident illumination.

Nano-confinement of block copolymers in high accuracy topographical guiding patterns: modelling the emergence of defectivity due to incommensurability.

Extreme ultraviolet interference lithography (EUV-IL) is used to manufacture topographical guiding patterns to direct the self-assembly of block copolymers. High-accuracy silicon oxide-like patterns with trenches ranging from 68 nm to 117 nm width are fabricated by exposing a hydrogen silsesquioxane (HSQ) resist layer using EUV-IL. We investigate how the accuracy, the low line width roughness and the low line edge roughness of the resulting patterns allow achieving DSA line/space patterns of a PS-b-PMMA (polystyrene-block-poly methyl methacrylate) block copolymer of 11 nm half-pitch with low defectivity. We conduct an in-depth study of the dependence of the DSA pattern morphology on the trench width and on how the neutral brush covers the guiding pattern. We identify the relation between trench width and the emergence of defects with nanometer precision. Based on these studies, we develop a model that extends available free energy models, which allows us to predict the patterning process window.

Changes in the near edge x-ray absorption fine structure of hybrid organic-inorganic resists upon exposure.

We report on the near edge x-ray absorption fine structure (NEXAFS) spectroscopy of hybrid organic-inorganic resists. These materials are nonchemically amplified systems based on Si, Zr, and Ti oxides, synthesized from organically modified precursors and transition metal alkoxides by a sol-gel route and designed for ultraviolet, extreme ultraviolet (EUV) and electron beam lithography. The experiments were conducted using a scanning transmission x-ray microscope (STXM) which combines high spatial-resolution microscopy and NEXAFS spectroscopy. The absorption spectra were collected in the proximity of the carbon edge (∼290 eV) before and after in situ exposure, enabling the measurement of a significant photo-induced degradation of the organic group (phenyl or methyl methacrylate, respectively), the degree of which depends on the configuration of the ligand. Photo-induced degradation was more efficient in the resist synthesized with pendant phenyl substituents than it was in the case of systems based on bridging phenyl groups. The degradation of the methyl methacrylate group was relatively efficient, with about half of the initial ligands dissociated upon exposure. Our data reveal that such dissociation can produce different outcomes, depending on the structural configuration. While all the organic groups were expected to detach and desorb from the resist in their entirety, a sizeable amount of them remained and formed undesired byproducts such as alkene chains. In the framework of the materials synthesis and engineering through specific building blocks, these results provide a deeper insight into the photochemistry of resists, in particular for EUV lithography.

State-of-the-art Nanofabrication in Catalysis.

We present recent developments in top-down nanofabrication that have found application in catalysis research. To unravel the complexity of catalytic systems, the design and use of models with control of size, morphology, shape and inter-particle distances is a necessity. The study of well-defined and ordered nanoparticles on a support contributes to the understanding of complex phenomena that govern reactions in heterogeneous and electro-catalysis. We review the strengths and limitations of different nanolithography methods such as electron beam lithography (EBL), photolithography, extreme ultraviolet (EUV) lithography and colloidal lithography for the creation of such highly tunable catalytic model systems and their applications in catalysis. Innovative strategies have enabled particle sizes reaching dimensions below 10 nm. It is now possible to create pairs of particles with distance controlled with an extremely high precision in the order of one nanometer. We discuss our approach to study these model systems at the single-particle level using X-ray absorption spectroscopy and show new ways to fabricate arrays of single nanoparticles or nanoparticles in pairs over a large area using EBL and EUV-achromatic Talbot lithography. These advancements have provided new insights into the active sites in metal catalysts and enhanced the understanding of the role of inter-particle interactions and catalyst supports, such as in the phenomenon of hydrogen spillover. We present a perspective on future directions for employing top-down nanofabrication in heterogeneous and electrocatalysis. The rapid development in nanofabrication and characterization methods will continue to have an impact on understanding of complex catalytic processes.

Enhancement of the intrinsic fluorescence of adenine using aluminum nanoparticle arrays.

This study demonstrates the metal-enhanced fluorescence of adenine using aluminum nanoparticle arrays in the deep UV range. It achieves the reproducible intensity enhancement of intrinsic fluorescence up to 80 on well-defined aluminum nanoparticle arrays at 257 nm excitation. In addition to a high signal enhancement, a strong modification of the fluorescence emission spectrum of adenine is observed. This study illustrates that the label-free detection of DNA bases and proteins that have low intrinsic fluorescence and absorption bands in the deep UV range can be facilitated using aluminum nanostructures.

Towards deep-UV surface-enhanced resonance Raman spectroscopy of explosives: ultrasensitive, real-time and reproducible detection of TNT.

We report ultrasensitive and label-free detection of 2,4,6-trinitrotoluene (TNT) deposited by drop coating using deep-ultraviolet surface-enhanced resonance Raman scattering (DUV-SERRS). Well-defined aluminum nanoparticle arrays as the SERRS substrate at 257 nm excitation wavelength enabled highly reproducible and real-time detection of TNT down to the detection limit of the attogram level in quantity. This extreme sensitivity can be further improved by optimization of the nanostructured substrates. DUV-SERRS promises to have a large impact on public safety and security, as it can be readily extended to other explosives and hazardous materials.

Broadband interference lithography at extreme ultraviolet and soft x-ray wavelengths.

Manufacturing efficient and broadband optics is of high technological importance for various applications in all wavelength regimes. Particularly in the extreme ultraviolet and soft x-ray spectra, this becomes challenging due to the involved atomic absorption edges that rapidly change the optical constants in these ranges. Here we demonstrate a new interference lithography grating mask that can be used for nanopatterning in this spectral range. We demonstrate photolithography with cutting-edge resolution at 6.5 and 13.5 nm wavelengths, relevant to the semiconductor industry, as well as using 2.5 and 4.5 nm wavelength for patterning thick photoresists and fabricating high-aspect-ratio metal nanostructures for plasmonics and sensing applications.

The choice of invasive diagnostic techniques in advanced lung cancer.

BACKGROUND: We retrospectively evaluated the invasive diagnostic techniques that were not suitable for transthoracic biopsy or bronchoscopy and the results of these techniques for advanced lung cancer cases. METHODS: The files of patients operated at the Department of Thoracic Surgery, Faculty of Medicine, Pamukkale University for advanced lung cancer (stages III and IV) between 2006 and 2010 were retrospectively reviewed for the analysis of definite diagnostic methods. RESULTS: The mean age of 59 patients who underwent invasive diagnostic techniques was 56.55 ± 9.42 years (32 to 75) and the female to male ratio was 1:4 (11 female:48 male). Mediastinoscopy was the most commonly used invasive technique with 20 patients (34%) while the second most common technique was video-assisted thoracoscopic surgery with 10 patients (17%). Thoracotomy was the most invasive diagnostic technique with four patients (6.5%). CONCLUSIONS: Although it would be desirable to use noninvasive and minimally invasive diagnostic techniques in the diagnosis of lung cancers, we should not try to avoid using invasive diagnostic techniques in surgical practice in advanced lung cancers where other techniques may be inadequate.

Gap plasmons and near-field enhancement in closely packed sub-10 nm gap resonators.

Pairs of metal nanoparticles with a sub-10 nm gap are an efficient way to achieve extreme near-field enhancement for sensing applications. We demonstrate an attractive alternative based on Fabry-Perot type nanogap resonators, where the resonance is defined by the gap width and vertical elongation instead of the particle geometry. We discuss the crucial design parameters for such gap plasmons to produce maximum near-field enhancement for surface-enhanced Raman scattering and show compatibility of the pattern processing with low-cost and low-resolution lithography. We find a minimum critical metal thickness of 80 nm and observe that the mode coupling from the far field increases by tapering the gap opening. We also show the saturation of the Raman signal for nanogap periodicities below 1 µm, demonstrating efficient funneling of light into such nanogap arrays.

Magnetic hot spots in closely spaced thick gold nanorings.

Light-matter interaction at optical frequencies is mostly mediated by the electric component of the electromagnetic field, with the magnetic component usually being considered negligible. Recently, it has been shown that properly engineered metallic nanostructures can provide a magnetic response at optical frequencies originated from real or virtual flows of electric current in the structure. In this work, we demonstrate a magnetic plasmonic mode which emerges in closely spaced thick gold nanorings. The plasmonic resonance obtains a magnetic dipole character by sufficiently increasing the height of the nanorings. Numerical simulations show that a virtual current loop appears at resonance for sufficiently thick nanorings, resulting in a strong concentration of the magnetic field in the gap region (magnetic hot spot). We find that there is an optimum thickness that provides the maximum magnetic intensity enhancement (over 200-fold enhancement) and give an explanation of this observation. This strong magnetic resonance, observed both experimentally and theoretically, can be used to build new metamaterials and resonant loop nanoantennas at optical frequencies.

The effect of different taping techniques on transtibial amputation walking parameters: A case report.

Buerger disease is a nonatherosclerotic, segmental inflammatory disease of the occlusive tract, often involving medium-sized muscular and small-diameter arteries and veins of the extremities. If medical treatment is not successful, amputation is inevitable. The aim of this study was to investigate the effect of different kinesiological taping techniques on walking parameters of transtibial amputee with knee extension limitation. Two different kinesiological taping methods (Kinesio Tape and Dynamic Tape) were applied to the transtibial patient with knee extension limitation. Walking performance of patients was assessed with The Biodex Gait Trainer 2. Gait parameters without tape were as follows: average walking speed 0.38 m/s, average step cycle 0.48 cyl/s, average left step length 50 cm, average right step length 43 cm, coefficient of variation 9% at the left, and coefficient of variation 9% at the right. After applying Kinesio Tape and Dynamic Tape, these values were measured as follows: average walking speed 0.50.56 m/s, average step cycle 0.51.56 cyl/s, average left step length 61-60 cm, average right step length 53-54 cm, coefficient of variation 6%-5% at the left, and coefficient of variation 6%-4% at the right side. Dynamic Tape and Kinesio Tape both had positive effects on active joint motion and walking parameters. Regarding walking speed and step length, Dynamic Tape was found to be more effective than Kinesio Tape. Taping methods applied to amputees have positive effects on range of motion, which in return causes improvements on walking parameters.

Three-Dimensional Microfluidic Capillary Device for Rapid and Multiplexed Immunoassays in Whole Blood.

In this study, we demonstrate whole blood immunoassays using a microfluidic device optimized for conducting rapid and multiplexed fluorescence-linked immunoassays. The device is capable of handling whole blood samples without any preparatory treatment. The three-dimensional channels in poly(methyl methacrylate) are designed to passively load bodily fluids and, due to their linearly tapered profile, facilitate size-dependent immobilization of biofunctionalized particles. The channel geometry is optimized to allow for the unimpeded flow of cellular constituents such as red blood cells (RBCs). Additionally, to make the device easier to operate, the biofunctionalized particles are pretrapped in a first step, and the channel is dried under vacuum, after which it can be loaded with the biological sample. This novel approach and design eliminated the need for traditionally laborious steps such as filtering, incubation, and washing steps, thereby substantially simplifying the immunoassay procedures. Moreover, by leveraging the shallow device dimensions, we show that sample loading to read-out is possible within 5 min. Our results also show that the presence of RBCs does not compromise the sensitivity of the assays when compared to those performed in a pure buffer solution. This highlights the practical adaptability of the device for simple and rapid whole-blood assays. Lastly, we demonstrate the device's multiplexing capability by pretrapping particles of different sizes, each functionalized with a different antigen, thus enabling the performance of multiplexed on-chip whole-blood immunoassays, showcasing the device's versatility and effectiveness toward low-cost, simple, and multiplexed sensing of biomarkers and pathogens directly in whole blood.

Recovery of spatial frequencies in coherent diffraction imaging in the presence of a central obscuration.

Coherent diffraction imaging (CDI) and its scanning version, ptychography, are lensless imaging approaches used to iteratively retrieve a sample's complex scattering amplitude from its measured diffraction patterns. These imaging methods are most useful in extreme ultraviolet (EUV) and X-ray regions of the electromagnetic spectrum, where efficient imaging optics are difficult to manufacture. CDI relies on high signal-to-noise ratio diffraction data to recover the phase, but increasing the flux can cause saturation effects on the detector. A conventional solution to this problem is to place a beam stop in front of the detector. The pixel masking method is a common solution to the problem of missing frequencies due to a beam stop. This paper describes the information redundancy in the recorded data set and expands on how the reconstruction algorithm can exploit this redundancy to estimate the missing frequencies. Thereafter, we modify the size of the beam stop in experimental and simulation data to assess the impact of the missing frequencies, investigate the extent to which the lost portion of the diffraction spectrum can be recovered, and quantify the effect of the beam stop on the image quality. The experimental findings and simulations conducted for EUV imaging demonstrate that when using a beam stop, the numerical aperture of the condenser is a crucial factor in the recovery of lost frequencies. Our thorough investigation of the reconstructed images provides information on the overall quality of reconstruction and highlights the vulnerable frequencies if the beam stop size is larger than the extent of the illumination NA. The outcome of this study can be applied to other sources of frequency loss, and it will contribute to the improvement of experiments and reconstruction algorithms in CDI.

EUV-induced hydrogen desorption as a step towards large-scale silicon quantum device patterning.

Atomically precise hydrogen desorption lithography using scanning tunnelling microscopy (STM) has enabled the development of single-atom, quantum-electronic devices on a laboratory scale. Scaling up this technology to mass-produce these devices requires bridging the gap between the precision of STM and the processes used in next-generation semiconductor manufacturing. Here, we demonstrate the ability to remove hydrogen from a monohydride Si(001):H surface using extreme ultraviolet (EUV) light. We quantify the desorption characteristics using various techniques, including STM, X-ray photoelectron spectroscopy (XPS), and photoemission electron microscopy (XPEEM). Our results show that desorption is induced by secondary electrons from valence band excitations, consistent with an exactly solvable non-linear differential equation and compatible with the current 13.5 nm (~92 eV) EUV standard for photolithography; the data imply useful exposure times of order minutes for the 300 W sources characteristic of EUV infrastructure. This is an important step towards the EUV patterning of silicon surfaces without traditional resists, by offering the possibility for parallel processing in the fabrication of classical and quantum devices through deterministic doping.

Rare complication spontaneous pneumothorax and pneumomediastinum in COVID-19 patients: A single center experience.

INTRODUCTION: We aimed to describe the clinical characteristics and outcomes of patients with spontaneous pneumothorax (SPT) and pneumomediastinum (SPM) due to COVID-19 pneumonia. METHODOLOGY: This retrospective study evaluated inpatients at a COVID-19 pandemic hospital. Between March 11, 2020 and March 31, 2021, patients who developed complications of spontaneous pneumothorax (SPT) and pneumomediastinum (SPM) with a confirmed diagnosis of SARS-CoV-2 by polymerase chain reaction (PCR) method were included. RESULTS: Of the 6,528 hospitalized patients, nine developed complications of SPT and SPM, with an incidence of 0.14%. Four of these patients developed SPT, one developed SPM, one developed SPT + SPM + emphysema, and three developed SPT + SPM. The mean age of the patients was 67.67 ± 13.41 years and the median was 68 (45-88) years. All patients were male. Six patients died, one of whom died of myocardial infarction from uncomplicated causes. CONCLUSIONS: Studies with more cases are needed to evaluate the causality between COVID-19 and pneumothorax (PT) and pneumomediastinum (PM). However, it should be kept in mind that PT and PM may lead to this clinic when sudden respiratory distress occurs in these patients and rapid diagnosis and treatment should be planned. As observed in this study, PT and PM are important factors in the development of mortality in COVID-19 patients.

Investigation of the correlation between knee joint position sense and physical functional performance in individuals with transtibial amputation.

INTRODUCTION: In individuals with transtibial amputation, the distal part of the lower extremity is lost. Therefore, the knee joint is of greater importance to be able to provide physical performance. The aim of this study was to evaluate the correlation between knee joint position sense and physical functional performance in individuals with transtibial amputation. METHODS: The study included 21 subjects with transtibial amputation. A digital inclinometer was used to evaluate the joint position sense of the amputated side knee joint. The timed up and go test, the 4-square step test, and 10-m walk test were used to evaluate physical functional performance. Linear regression analysis was used to investigate the associations between independent variables and functional performance tests. RESULTS: The mean age of the participants was 52.52 ± 15.68 years. The mean of the error in knee joint position sense was 5.33 degree (standard deviation = 3.08 degree). The error in knee joint position sense of the amputated limb predicted 45% of the variance in the 4-square step test and 22% of the variance in the 10-m walk test ( P < 0.05). CONCLUSIONS: The knee joint position sense on the amputated side was found to be associated with physical functional performance in individuals with transtibial amputation. Residual limb knee joint position sense should be considered when prescribing prostheses and planning rehabilitation programs.