Enhanced Photocatalytic Properties and Photoinduced Crystallization of TiO2-Fe2O3 Inverse Opals Fabricated by Atomic Layer Deposition.

The use of solar energy for photocatalysis holds great potential for sustainable pollution reduction. Titanium dioxide (TiO2) is a benchmark material, effective under ultraviolet light but limited in visible light utilization, restricting its application in solar-driven photocatalysis. Previous studies have shown that semiconductor heterojunctions and nanostructuring can broaden the TiO2's photocatalytic spectral range. Semiconductor heterojunctions are interfaces formed between two different semiconductor materials that can be engineered. Especially, type II heterojunctions facilitate charge separation, and they can be obtained by combining TiO2 with, for example, iron(III) oxide (Fe2O3). Nanostructuring in the form of 3D inverse opals (IOs) demonstrated increased TiO2 light absorption efficiency of the material, by tailoring light-matter interactions through their photonic crystal structure and specifically their photonic stopband, which can give rise to a slow photon effect. Such effect is hypothesized to enhance the generation of free charges. This work focuses on the above-described effects simultaneously, through the synthesis of TiO2-Fe2O3 IOs via multilayer atomic layer deposition (ALD) and the characterization of their photocatalytic activities. Our results reveal that the complete functionalization of TiO2 IOs with Fe2O3 increases the photocatalytic activity through the slow photon effect and semiconductor heterojunction formation. We systematically explore the influence of Fe2O3 thickness on photocatalytic performance, and a maximum photocatalytic rate constant of 1.38 ± 0.09 h-1 is observed for a 252 nm template TiO2-Fe2O3 bilayer IO consisting of 16 nm TiO2 and 2 nm Fe2O3. Further tailoring the performance by overcoating with additional TiO2 layers enhances photoinduced crystallization and tunes photocatalytic properties. These findings highlight the potential of TiO2-Fe2O3 IOs for efficient water pollutant removal and the importance of precise nanostructuring and heterojunction engineering in advancing photocatalytic technologies.

Quantum Dot/TiO2 Nanocomposite-Based Photoelectrochemical Sensor for Enhanced H2O2 Detection Applied for Cell Monitoring and Visualization.

This work exploits the possibility of using CdSe/ZnS quantum dot (QD)-electrodes to monitor the metabolism of living cells based on photoelectrochemical (PEC) measurements. To realize that, the PEC setup is improved with respect to an enhanced photocurrent signal, better stability, and an increased signal-to-noise ratio, but also for a better biocompatibility of the sensor surface on which cells have been grown. To achieve this, a QD-TiO2 heterojunction is introduced with the help of atomic layer deposition (ALD). The heterojunction reduces the charge carrier recombination inside the semiconductor nanoparticles and improves the drift behavior. The PEC performance is carefully analyzed by adjusting the TiO2 thickness and combining this strategy with multilayer immobilizations of QDs. The optimal thickness of this coating is ≈5 nm; here, photocurrent generation can be enhanced significantly (e.g., for a single QD layer electrode by more than one order of magnitude at 0 V vs Ag/AgCl). The resulting optimized electrode is used for hydrogen peroxide (H2O2) sensing with a good sensitivity down to µmolar concentrations, reusability, stability, response rate, and repeatability. Finally, the sensing system is applied to monitor the activity of cells directly grown on top of the electrode surface.

Controlled Synthesis of Terbium-Doped Colloidal Gd2O2S Nanoplatelets Enables High-Performance X-ray Scintillators.

Terbium-doped gadolinium oxysulfide (Gd2O2S:Tb3+), commonly referred to as Gadox, is a widely used scintillator material due to its exceptional X-ray attenuation efficiency and high light yield. However, Gadox-based scintillators suffer from low X-ray spatial resolution due to their large particle size, which causes significant light scattering. To address this limitation, we report the synthesis of terbium-doped colloidal Gadox nanoplatelets (NPLs) with near-unity photoluminescence quantum yield (PLQY) and high radioluminescence light yield (LY). In particular, our investigation reveals a strong correlation between PLQY, LY, particle size, and Tb3+concentration. Our synthetic approach allows precise control over the lateral size and thickness of the Gadox NPLs, resulting in a LY of 50,000 photons/MeV. Flexible scintillating screens fabricated with the solution-processable Gadox NPLs exhibited a 20 lp/mm X-ray spatial resolution, surpassing commercial Gadox scintillators. These high-performance and flexible Gadox NPL-based scintillators enable enhanced X-ray imaging capabilities in medicine and security. Our work provides a framework for designing nanomaterial scintillators with superior spatial resolution and efficiency through precise control of dimensions and dopant concentration.

Correction to "Thermally Driven Field Emission from ZnO Wires on a Nanomembrane Used as a Detector for Time-of-Flight Mass Spectrometry".

[This corrects the article DOI: 10.1021/acsomega.3c08932.].

GaAs Cone-Shell Quantum Dots in a Lateral Electric Field: Exciton Stark-Shift, Lifetime, and Fine-Structure Splitting.

Strain-free GaAs cone-shell quantum dots have a unique shape, which allows a wide tunability of the charge-carrier probability densities by external electric and magnetic fields. Here, the influence of a lateral electric field on the optical emission is studied experimentally using simulations. The simulations predict that the electron and hole form a lateral dipole when subjected to a lateral electric field. To evaluate this prediction experimentally, we integrate the dots in a lateral gate geometry and measure the Stark-shift of the exciton energy, the exciton intensity, the radiative lifetime, and the fine-structure splitting (FSS) using single-dot photoluminescence spectroscopy. The respective gate voltage dependencies show nontrivial trends with three pronounced regimes. We assume that the respective dominant processes are charge-carrier deformation at a low gate voltage U, a vertical charge-carrier shift at medium U, and a lateral charge-carrier polarization at high U. The lateral polarization forms a dipole, which can either enhance or compensate the intrinsic FSS induced by the QD shape anisotropy, dependent on the in-plane orientation of the electric field. Furthermore, the data show that the biexciton peak can be suppressed by a lateral gate voltage, and we assume the presence of an additional vertical electric field induced by surface charges.

Field Emission from Carbon Nanotubes on Titanium Nitride-Coated Planar and 3D-Printed Substrates.

Carbon nanotubes (CNTs) are well known for their outstanding field emission (FE) performance, facilitated by their unique combination of electrical, mechanical, and thermal properties. However, if the substrate of choice is a poor conductor, the electron supply towards the CNTs can be limited, restricting the FE current. Furthermore, ineffective heat dissipation can lead to emitter-substrate bond degradation, shortening the field emitters' lifetime. Herein, temperature-stable titanium nitride (TiN) was deposited by plasma-enhanced atomic layer deposition (PEALD) on different substrate types prior to the CNT growth. A turn-on field reduction of up to 59% was found for the emitters that were generated on TiN-coated bulk substrates instead of on pristine ones. This observation was attributed exclusively to the TiN layer as no significant change in the emitter morphology could be identified. The fabrication route and, consequently, improved FE properties were transferred from bulk substrates to free-standing, electrically insulating nanomembranes. Moreover, 3D-printed, polymeric microstructures were overcoated by atomic layer deposition (ALD) employing its high conformality. The results of our approach by combining ALD with CNT growth could assist the future fabrication of highly efficient field emitters on 3D scaffold structures regardless of the substrate material.

Thermally Driven Field Emission from Zinc Oxide Wires on a Nanomembrane Used as a Detector for Time-of-Flight Mass Spectrometry.

Mass spectrometry is a crucial technology in numerous applications, but it places stringent requirements on the detector to achieve high resolution across a broad spectrum of ion masses. Low-dimensional nanostructures offer opportunities to tailor properties and achieve performance not reachable in bulk materials. Here, an array of sharp zinc oxide wires was directly grown on a 30 nm thin, free-standing silicon nitride nanomembrane to enhance its field emission (FE). The nanomembrane was subsequently used as a matrix-assisted laser desorption/ionization time-of-flight mass spectrometry detector. When ionized biomolecules impinge on the backside of the surface-modified nanomembrane, the current-emitted from the wires on the membrane's front side-is amplified by the supplied thermal energy, which allows for the detection of the ions. An extensive simulation framework was developed based on a combination of lateral heat diffusion in the nanomembrane, heat diffusion along the wires, and FE, including Schottky barrier lowering, to investigate the impact of wire length and diameter on the FE. Our theoretical model suggests a significant improvement in the overall FE response of the nanomembrane by growing wires on top. Specifically, long thin wires are ideal to enhance the magnitude of the FE signal and to shorten its duration for the fastest response simultaneously, which could facilitate the future application of detectors in mass spectrometry with properties improved by low-dimensional nanostructures.

Temperature-Enhanced Exciton Emission from GaAs Cone-Shell Quantum Dots.

The temperature-dependent intensities of the exciton (X) and biexciton (XX) peaks from single GaAs cone-shell quantum dots (QDs) are studied with micro photoluminescence (PL) at varied excitation power and QD size. The QDs are fabricated by filling self-assembled nanoholes, which are drilled in an AlGaAs barrier by local droplet etching (LDE) during molecular beam epitaxy (MBE). This method allows the fabrication of strain-free QDs with sizes precisely controlled by the amount of material deposited for hole filling. Starting from the base temperature T = 3.2 K of the cryostat, single-dot PL measurements demonstrate a strong enhancement of the exciton emission up to a factor of five with increasing T. Both the maximum exciton intensity and the temperature Tx,max of the maximum intensity depend on excitation power and dot size. At an elevated excitation power, Tx,max becomes larger than 30 K. This allows an operation using an inexpensive and compact Stirling cryocooler. Above Tx,max, the exciton intensity decreases strongly until it disappears. The experimental data are quantitatively reproduced by a model which considers the competing processes of exciton generation, annihilation, and recombination. Exciton generation in the QDs is achieved by the sum of direct excitation in the dot, plus additional bulk excitons diffusing from the barrier layers into the dot. The thermally driven bulk-exciton diffusion from the barriers causes the temperature enhancement of the exciton emission. Above Tx,max, the intensity decreases due to exciton annihilation processes. In comparison to the exciton, the biexciton intensity shows only very weak enhancement, which is attributed to more efficient annihilation processes.

Booster-microchannel plate (BMCP) detector for signal amplification in MALDI-TOF mass spectrometry for ions beyond m/z 50 000.

Top-down proteomics deals with the characterization of intact biomolecules, which reduces the sample complexity and facilitates the detection of modifications at the protein level. The combination of the matrix-assisted laser desorption/ionization (MALDI) technique with time-of-flight (TOF) mass analysis allows for the generation of gaseous ions in low charge states from high-mass biomolecules, followed by their mass-to-charge ratio (m/z) separation, as high-mass ions drift down the flight tube more slowly than lighter ones. However, the detection efficiency of conventional microchannel plate (MCP) detectors is strongly reduced with decreasing ion velocity-corresponding to an increase in ion mass-which impedes the reliable detection of high-mass biomolecules. Herein, we present a simple modification of the MCP detector that allows for the amplification of the signal from ionized proteins of up to m/z 150 000. Two circular electrodes were assembled in front of the conventional detector and set to negative electrical voltages to affect the positively charged ions directly before they impinge on the MCP, possibly through a combination of a velocity boost and ion optical effects. In the present study, three booster electrode configurations were experimentally tested to maximize the signal intensification. Compared to the conventional MCP assembly, the signal intensity was amplified in a proof-of-concept experiment by a factor of 24.3 and of 10.7 for the singly charged BSA ion (m/z 66 400) and for the singly charged IgG ion (m/z 150 000), respectively, by applying the booster-MCP (BMCP) detector.

Plasmonic hot carrier injection from single gold nanoparticles into topological insulator Bi2Se3 nanoribbons.

Plasmonic gold nanoparticles injecting hot carriers into the topological insulator (TI) interface of Bi2Se3 nanoribbons are studied by resonant Raman spectroscopy. We resolve the impact of individual gold particles with sizes ranging from 140 nm down to less than 40 nm on the topological surface states of the nanoribbons. In resonance at 1.96 eV (633 nm), we find distinct phonon renormalization in the Eg2- and A1g2-modes that can be associated with plasmonic hot carrier injection. The phonon modes are strongly enhanced by a factor of 350 when tuning the excitation wavelengths into interband transition and in resonance with the surface plasmon of gold nanoparticles. At 633 nm wavelength, a plasmonic enhancement factor of 18 is observed indicating a contribution of hot carriers injected from the gold nanoparticles into the TI interface. Raman studies as a function of gold nanoparticle size reveal the strongest hot carrier injection for particles with size of 108 nm in agreement with the resonance energy of its surface plasmon. Hot carrier injection opens the opportunity to locally control the electronic properties of the TI by metal nanoparticles attached to the surface of nanoribbons.

Carrier Injection Observed by Interface-Enhanced Raman Scattering from Topological Insulators on Gold Substrates.

The electron-phonon interaction at the interface between topological insulator (TI), namely, Bi2Se3 and Bi2Te3 two-dimensional (2D) nanoflakes, to a gold substrate as a function of TI flake thickness is studied by means of Raman scattering. We reveal the presence of interface-enhanced Raman scattering and a strong phonon renormalization induced by carriers injected from the gold substrate to the topological surface in contact. We derive the change of the electron-phonon coupling showing a nearly linear behavior as a function of layer thickness. The strongly nonlinear change of the Raman scattering cross section as a function of flake thickness can be associated with band bending effects at the metal-TI interface. Our results provide spectroscopic evidence for a strongly modified band structure in the first few quintuple layers of Bi2Se3 and Bi2Te3 in contact with gold.

Acoustically Induced Giant Synthetic Hall Voltages in Graphene.

Any departure from graphene's flatness leads to the emergence of artificial gauge fields that act on the motion of the Dirac fermions through an associated pseudomagnetic field. Here, we demonstrate the tunability of strong gauge fields in nonlocal experiments using a large planar graphene sheet that conforms to the deformation of a piezoelectric layer by a surface acoustic wave. The acoustic wave induces a longitudinal and a giant synthetic Hall voltage in the absence of external magnetic fields. The superposition of a synthetic Hall potential and a conventional Hall voltage can annihilate the sample's transverse potential at large external magnetic fields. Surface acoustic waves thus provide a promising and facile avenue for the exploitation of gauge fields in large planar graphene systems.

Subtractive Low-Temperature Preparation Route for Porous SiO2 Used for the Catalyst-Assisted Growth of ZnO Field Emitters.

The possibility to gradually increase the porosity of thin films facilitates a variety of applications, such as anti-reflective coatings, diffusion membranes, and the herein investigated tailored nanostructuring of a substrate for subsequent self-assembly processes. A low-temperature (<160 °C) preparation route for porous silicon oxide (porSiO2) thin films with porosities of about 60% and effective refractive indices down to 1.20 is tailored for bulk as well as free-standing membranes. Subsequently, both substrate types are successfully employed for the catalyst-assisted growth of nanowire-like zinc oxide (ZnO) field emitters by metal organic chemical vapor deposition. ZnO nanowires can be grown with a large aspect ratio and exhibit a good thermal and chemical stability, which makes them excellent candidates for field emitter arrays. We present a method that allows for the direct synthesis of nanowire-like ZnO field emitters on free-standing membranes using a porSiO2 template. Besides the application of porSiO2 for the catalyst-assisted growth of nanostructures and their use as field emission devices, the herein presented general synthesis route for the preparation of low refractive index films on other than bulk substrates-such as on free-standing, ultra-thin membranes-may pave the way for the employment of porSiO2 in micro-electro-mechanical systems.

Culturing human iPSC-derived neural progenitor cells on nanowire arrays: mapping the impact of nanowire length and array pitch on proliferation, viability, and membrane deformation.

Nanowire arrays used as cell culture substrates build a potent tool for advanced biological applications such as cargo delivery and biosensing. The unique topography of nanowire arrays, however, renders them a challenging growth environment for cells and explains why only basic cell lines have been employed in existing studies. Here, we present the culturing of human induced pluripotent stem cell-derived neural progenitor cells on rectangularly arranged nanowire arrays: In detail, we mapped the impact on proliferation, viability, and topography-induced membrane deformation across a multitude of array pitches (1, 3, 5, 10 µm) and nanowire lengths (1.5, 3, 5 µm). Against the intuitive expectation, a reduced proliferation was found on the arrays with the smallest array pitch of 1 µm and long NWs. Typically, cells settle in a fakir-like state on such densely-spaced nanowires and thus experience no substantial stress caused by nanowires indenting the cell membrane. However, imaging of F-actin showed a distinct reorganization of the cytoskeleton along the nanowire tips in the case of small array pitches interfering with regular proliferation. For larger pitches, the cell numbers depend on the NW lengths but proliferation generally continued although heavy deformations of the cell membrane were observed caused by the encapsulation of the nanowires. Moreover, we noticed a strong interaction of the nanowires with the nucleus in terms of squeezing and indenting. Remarkably, the cell viability is maintained at about 85% despite the massive deformation of the cells. Considering the enormous potential of human induced stem cells to study neurodegenerative diseases and the high cellular viability combined with a strong interaction with nanowire arrays, we believe that our results pave the way to apply nanowire arrays to human stem cells for future applications in stem cell research and regenerative medicine.

Mechanically Modulated Sideband and Squeezing Effects of Membrane Resonators.

We investigate the sideband spectra of a driven nonlinear mode with its eigenfrequency being modulated at a low frequency (<1 kHz). This additional parametric modulation leads to prominent antiresonance line shapes in the sideband spectra, which can be controlled through the vibration state of the driven mode. We also establish a direct connection between the antiresonance frequency and the squeezing of thermal fluctuation in the system. Our Letter not only provides a simple and robust method for squeezing characterization, but also opens a new possibility toward sideband applications.

Robust neuronal differentiation of human iPSC-derived neural progenitor cells cultured on densely-spaced spiky silicon nanowire arrays.

Nanostructured cell culture substrates featuring nanowire (NW) arrays have been applied to a variety of basic cell lines and rodent neurons to investigate cellular behavior or to stimulate cell responses. However, patient-derived human neurons-a prerequisite for studying e.g. neurodegenerative diseases efficiently-are rarely employed due to sensitive cell culture protocols and usually long culturing periods. Here, we present human patient induced pluripotent stem cell-derived neurons cultured on densely-spaced spiky silicon NW arrays (600 NWs/ 100 µm[Formula: see text] with NW lengths of 1 µm) which show mature electrophysiological characteristics after only 20 days of culturing. Exemplary neuronal growth and network formation on the NW arrays are demonstrated using scanning electron microscopy and immunofluorescence microscopy. The cells and neurites rest in a fakir-like settling state on the NWs only in contact with the very NW tips shown by cross-sectional imaging of the cell/NW interface using focused ion beam milling and confocal laser scanning microscopy. Furthermore, the NW arrays promote the cell culture by slightly increasing the share of differentiated neurons determined by the quantification of immunofluorescence microscopy images. The electrophysiological functionality of the neurons is confirmed with patch-clamp recordings showing the excellent capability to fire action potentials. We believe that the short culturing time to obtain functional human neurons generated from patient-derived neural progenitor cells and the robustness of this differentiation protocol to produce these neurons on densely-spaced spiky nanowire arrays open up new pathways for stem cell characterization and neurodegenerative disease studies.

Direct writing of colloidal suspensions onto inclined surfaces: Optimizing dispense volume for homogeneous structures.

HYPOTHESIS: A process to fabricate structures on inclined substrates has the potential to yield novel applications for colloidal-based structures. However, for conventional techniques, besides the coffee ring effect (CRE), anisotropic particle deposition along the inclination direction (IE) is expected to occur. We hypothesize that both effects can be inhibited by reducing the dispense volume during printing by direct writing. EXPERIMENTS: We combined an additive manufacturing technique, namely direct writing, with colloidal assembly (AMCA) for an automated and localized drop-cast of polystyrene and silica suspensions onto inclined surfaces. Herein, we investigated the influence of the substrate tilting angle and the dispense volume on the printing of colloids and the resulting structures' morphology. FINDINGS: The results demonstrate that a reduction in the dispense volume hinders the CRE and IE for both particles' systems, even though the evaporation mode is different. For polystyrene, the droplets evaporated solely in stick-mode, enabling a "surface capturing effect", while for silica, droplets evaporated in mixed stick-slip mode and a "confinement effect" was observed, which improved uniformity of the deposition. These findings were used to generate a model of the critical droplet radius needed to print homogeneous colloidal-based structures onto inclined substrates.

Influence of Alumina Addition on the Optical Properties and the Thermal Stability of Titania Thin Films and Inverse Opals Produced by Atomic Layer Deposition.

TiO2 thin films deposited by atomic layer deposition (ALD) at low temperatures (<100 °C) are, in general, amorphous and exhibit a smaller refractive index in comparison to their crystalline counterparts. Nonetheless, low-temperature ALD is needed when the substrates or templates are based on polymeric materials, as the deposition has to be performed below their glass transition or melting temperatures. This is the case for photonic crystals generated via ALD infiltration of self-assembled polystyrene templates. When heated up, crystal phase transformations take place in the thin films or photonic structures, and the accompanying volume reduction as well as the burn-out of residual impurities can lead to mechanical instability. The introduction of cation doping (e.g., Al or Nb) in bulk TiO2 parts is known to alter phase transitions and to stabilize crystalline phases. In this work, we have developed low-temperature ALD super-cycles to introduce Al2O3 into TiO2 thin films and photonic crystals. The aluminum oxide content was adjusted by varying the TiO2:Al2O3 internal loop ratio within the ALD super-cycle. Both thin films and inverse opal photonic crystal structures were subjected to thermal treatments ranging from 200 to 1200 °C and were characterized by in- and ex-situ X-ray diffraction, spectroscopic ellipsometry, and spectroscopic reflectance measurements. The results show that the introduction of alumina affects the crystallization and phase transition temperatures of titania as well as the optical properties of the inverse opal photonic crystals (iPhC). The thermal stability of the titania iPhCs was increased by the alumina introduction, maintaining their photonic bandgap even after heat treatment at 900 °C and outperforming the pure titania, with the best results being achieved with the super-cycles corresponding to an estimated alumina content of 26 wt.%.

X-ray-Based Techniques to Study the Nano-Bio Interface.

X-ray-based analytics are routinely applied in many fields, including physics, chemistry, materials science, and engineering. The full potential of such techniques in the life sciences and medicine, however, has not yet been fully exploited. We highlight current and upcoming advances in this direction. We describe different X-ray-based methodologies (including those performed at synchrotron light sources and X-ray free-electron lasers) and their potentials for application to investigate the nano-bio interface. The discussion is predominantly guided by asking how such methods could better help to understand and to improve nanoparticle-based drug delivery, though the concepts also apply to nano-bio interactions in general. We discuss current limitations and how they might be overcome, particularly for future use in vivo.

Toward Brain-on-a-Chip: Human Induced Pluripotent Stem Cell-Derived Guided Neuronal Networks in Tailor-Made 3D Nanoprinted Microscaffolds.

Brain-on-a-chip (BoC) concepts should consider three-dimensional (3D) scaffolds to mimic the 3D nature of the human brain not accessible by conventional planar cell culturing. Furthermore, the essential key to adequately address drug development for human pathophysiological diseases of the nervous system, such as Parkinson's or Alzheimer's, is to employ human induced pluripotent stem cell (iPSC)-derived neurons instead of neurons from animal models. To address both issues, we present electrophysiologically mature human iPSC-derived neurons cultured in BoC applicable microscaffolds prepared by direct laser writing. 3D nanoprinted tailor-made elevated cavities interconnected by freestanding microchannels were used to create defined neuronal networks-as a proof of concept-with two-dimensional topology. The neuronal outgrowth in these nonplanar structures was investigated, among others, in terms of neurite length, size of continuous networks, and branching behavior using z-stacks prepared by confocal microscopy and cross-sectional scanning electron microscopy images prepared by focused ion beam milling. Functionality of the human iPSC-derived neurons was demonstrated with patch clamp measurements in both current- and voltage-clamp mode. Action potentials and spontaneous excitatory postsynaptic currents-fundamental prerequisites for proper network signaling-prove full integrity of these artificial neuronal networks. Considering the network formation occurring within only a few days and the versatile nature of direct laser writing to create even more complex scaffolds for 3D network topologies, we believe that our study offers additional approaches in human disease research to mimic the complex interconnectivity of the human brain in BoC studies.