Correlative Imaging of Individual CsPbBr3 Nanocrystals: Role of Isolated Grains in Photoluminescence of Perovskite Polycrystalline Thin Films.

We report on the optical properties of a CsPbBr3 polycrystalline thin film on a single grain level. A sample composed of isolated nanocrystals (NCs) mimicking the properties of the polycrystalline thin film grains that can be individually probed by photoluminescence spectroscopy was prepared. These NCs were analyzed using correlative microscopy allowing the examination of structural, chemical, and optical properties from identical sites. Our results show that the stoichiometry of the CsPbBr3 NCs is uniform and independent of the NCs' morphology. The photoluminescence (PL) peak emission wavelength is slightly dependent on the dimensions of NCs, with a blue shift up to 9 nm for the smallest analyzed NCs. The magnitude of the blueshift is smaller than the emission line width, thus detectable only by high-resolution PL mapping. By comparing the emission energies obtained from the experiment and a rigorous effective mass model, we can fully attribute the observed variations to the size-dependent quantum confinement effect.

Low temperature 2D GaN growth on Si(111) 7 × 7 assisted by hyperthermal nitrogen ions.

As the characteristic dimensions of modern top-down devices are getting smaller, such devices reach their operational limits imposed by quantum mechanics. Thus, two-dimensional (2D) structures appear to be one of the best solutions to meet the ultimate challenges of modern optoelectronic and spintronic applications. The representative of III-V semiconductors, gallium nitride (GaN), is a great candidate for UV and high-power applications at a nanoscale level. We propose a new way of fabrication of 2D GaN on the Si(111) 7 × 7 surface using post-nitridation of Ga droplets by hyperthermal (E = 50 eV) nitrogen ions at low substrate temperatures (T < 220 °C). The deposition of Ga droplets and their post-nitridation are carried out using an effusion cell and a special atom/ion beam source developed by our group, respectively. This low-temperature droplet epitaxy (LTDE) approach provides well-defined ultra-high vacuum growth conditions during the whole fabrication process resulting in unique 2D GaN nanostructures. A sharp interface between the GaN nanostructures and the silicon substrate together with a suitable elemental composition of nanostructures was confirmed by TEM. In addition, SEM, X-ray photoelectron spectroscopy (XPS), AFM and Auger microanalysis were successful in enabling a detailed characterization of the fabricated GaN nanostructures.

Replica-mold nanopatterned PHEMA hydrogel surfaces for ophthalmic applications.

Biomimicking native tissues and organs require the development of advanced hydrogels. The patterning of hydrogel surfaces may enhance the cellular functionality and therapeutic efficacy of implants. For example, nanopatterning of the intraocular lens (IOL) surface can suppress the upregulation of cytoskeleton proteins (actin and actinin) within the cells in contact with the IOL surface and, hence, prevent secondary cataracts causing blurry or opaque vision. Here we introduce a fast and efficient method for fabricating arrays consisting of millions of individual nanostructures on the hydrogel surface. In particular, we have prepared the randomly distributed nanopillars on poly(2-hydroxyethyl methacrylate) hydrogel using replica molding and show that the number, shape, and arrangement of nanostructures are fully adjustable. Characterization by atomic force microscopy revealed that all nanopillars were of similar shape, narrow size distribution, and without significant defects. In imprint lithography, choosing the appropriate hydrogel composition is critical. As hydrogels with imprinted nanostructures mimic the natural cell environment, they can find applications in fundamental cell biology research, e.g., they can tune cell attachment and inhibit or promote cell clustering by a specific arrangement of protrusive nanostructures on the hydrogel surface.

Tuning Magnetic Properties of a Carbon Nanotube-Lanthanide Hybrid Molecular Complex through Controlled Functionalization.

Molecular magnets attached to carbon nanotubes (CNT) are being studied as potential candidates for developing spintronic and quantum technologies. However, the functionalization routes used to develop these hybrid systems can drastically affect their respective physiochemical properties. Due to the complexity of this systems, little work has been directed at establishing the correlation between the degree of functionalization and the magnetic character. Here, we demonstrate the chemical functionalization degree associated with molecular magnet loading can be utilized for controlled tuning the magnetic properties of a CNT-lanthanide hybrid complex. CNT functionalization degree was evaluated by interpreting minor Raman phonon modes in relation to the controlled reaction conditions. These findings were exploited in attaching a rare-earth-based molecular magnet (Gd-DTPA) to the CNTs. Inductively coupled plasma mass spectrometry, time-of-flight secondary ion mass spectrometry and super conducting quantum interference device (SQUID) measurements were used to elucidate the variation of magnetic character across the samples. This controlled Gd-DTPA loading on the CNT surface has led to a significant change in the nanotube intrinsic diamagnetism, showing antiferromagnetic coupling with increase in the Weiss temperature with respect to increased loading. This indicates that synthesis of a highly correlated spin system for developing novel spintronic technologies can be realized through a carbon-based hybrid material.

Depth Profile Analysis of Thin Oxide Layers on Polycrystalline Fe-Cr.

Surfaces of polycrystalline ferritic Fe-Cr steel with grain sizes of about 13 µm in diameter were investigated with surface sensitive techniques. Thin oxide layers, with a maximum thickness of about 100 nm, were grown by oxidation in air at temperatures up to 450°C and were subsequently characterized using time-of-flight secondary ion mass spectrometry (TOF-SIMS) and atomic force microscopy. Correlative microscopy was applied, which allows for element-specific depth profiles on selected grains with a particular crystal orientation. A strong correlation between the grain orientation and the thickness of the oxide layer was found. The sequence in the oxidation growth rate of ferritic Fe-Cr steel crystal planes is found to be {011} > {111} > {001}, which is unexpectedly opposed to known Fe-based systems. Moreover, for the first time, the Cr/Fe ratio throughout the oxide layer has been determined per grain orientation. A clear order from high to low of {001} > {111} > {011} was detected.

Fundamentals of cathodoluminescence in a STEM: The impact of sample geometry and electron beam energy on light emission of semiconductors.

Cathodoluminescence has attracted interest in scanning transmission electron microscopy since the advent of commercial available detection systems with high efficiency, like the Gatan Vulcan or the Attolight Mönch system. In this work we discuss light emission caused by high-energy electron beams when traversing a semiconducting specimen. We find that it is impossible to directly interpret the spectrum of the emitted light to the inter-band transitions excited by the electron beam, because the Cerenkov effect and the related light guiding modes as well as transition radiation is altering the spectra. Total inner reflection and subsequent interference effects are changing the spectral shape dependent on the sample shape and geometry, sample thickness, and beam energy, respectively. A detailed study on these parameters is given using silicon and GaAs as test materials.

Near-field digital holography: a tool for plasmon phase imaging.

The knowledge of the phase distribution of the near electromagnetic field has become very important for many applications. However, its experimental observation is still technologically a very demanding task. In this work, we propose a novel method for the measurement of the phase distribution of the near electric field based on the principles of phase-shifting digital holography. In contrast to previous methods the holographic interference occurs already in the near field and the phase distribution can be determined purely from the scanning near-field optical microscopy measurements without the need for additional far-field interferometric methods. This opens a way towards on-chip phase imaging. We demonstrate the capabilities of the proposed method by reconstruction of the phase difference between interfering surface plasmon waves and by imaging the phase of a single surface plasmon wave. We also demonstrate a selectivity of the method towards individual components of the field.

Ideally Hexagonally Ordered TiO2 Nanotube Arrays.

Ideally hexagonally ordered TiO2 nanotube layers were produced through the optimized anodization of Ti substrates. The Ti substrates were firstly covered with a TiN protecting layer prepared through atomic layer deposition (ALD). Pre-texturing of the TiN-protected Ti substrate on an area of 20×20 µm2 was carried out by focused ion beam (FIB) milling, yielding uniform nanoholes with a hexagonal arrangement throughout the TiN layer with three different interpore distances. The subsequent anodic nanotube growth using ethylene-glycol-based electrolyte followed the pre-textured nanoholes, resulting in perfectly ordered nanotube layers (resembling honeycomb porous anodic alumina) without any point defects and with a thickness of approximately 2 µm over the whole area of the pattern.

Imaging of near-field interference patterns by aperture-type SNOM - influence of illumination wavelength and polarization state.

Scanning near-field optical microscopy (SNOM) in combination with interference structures is a powerful tool for imaging and analysis of surface plasmon polaritons (SPPs). However, the correct interpretation of SNOM images requires profound understanding of principles behind their formation. To study fundamental principles of SNOM imaging in detail, we performed spectroscopic measurements by an aperture-type SNOM setup equipped with a supercontinuum laser and a polarizer, which gave us all the degrees of freedom necessary for our investigation. The series of wavelength- and polarization-resolved measurements, together with results of numerical simulations, then allowed us to identify the role of individual near-field components in formation of SNOM images, and to show that the out-of-plane component generally dominates within a broad range of parameters explored in our study. Our results challenge the widespread notion that this component does not couple to the aperture-type SNOM probe and indicate that the issue of SNOM probe sensitivity towards the in-plane and out-of-plane near-field components - one of the most challenging tasks of near field interference SNOM measurements - is not yet fully resolved.

Nanometer-Sized Water Bridge and Pull-Off Force in AFM at Different Relative Humidities: Reproducibility Measurement and Model Based on Surface Tension Change.

This article deals with the analysis of the relationship between the pull-off force measured by atomic force microscopy and the dimensions of water bridge condensed between a hydrophilic silicon oxide tip and a silicon oxide surface under ambient conditions. Our experiments have shown that the pull-off force increases linearly with the radius of the tip and nonmonotonically with the relative humidity (RH). The latter dependence generally consists of an initial constant part changing to a convex-concave-like increase of the pull-off force and finally followed by a concave-like decrease of this force. The reproducibility tests have demonstrated that the precision limits have to be taken into account for comparing these measurements carried out under atmospheric conditions. The results were fitted by a classical thermodynamic model based on water-bridge envelope calculations using the numerical solution of the Kelvin equation in the form of axisymmetric differential equations and consequent calculation of adhesive forces. To describe the measured data more precisely, a decrease of the water surface tension for low RH was incorporated into the calculation. Such a decrease can be expected as a consequence of the high surface curvature in the nanometer-sized water bridge between the tip and the surface.

Optimization of ion-atomic beam source for deposition of GaN ultrathin films.

We describe the optimization and application of an ion-atomic beam source for ion-beam-assisted deposition of ultrathin films in ultrahigh vacuum. The device combines an effusion cell and electron-impact ion beam source to produce ultra-low energy (20-200 eV) ion beams and thermal atomic beams simultaneously. The source was equipped with a focusing system of electrostatic electrodes increasing the maximum nitrogen ion current density in the beam of a diameter of ≈15 mm by one order of magnitude (j ≈ 1000 nA/cm(2)). Hence, a successful growth of GaN ultrathin films on Si(111) 7 × 7 substrate surfaces at reasonable times and temperatures significantly lower (RT, 300 °C) than in conventional metalorganic chemical vapor deposition technologies (≈1000 °C) was achieved. The chemical composition of these films was characterized in situ by X-ray Photoelectron Spectroscopy and morphology ex situ using Scanning Electron Microscopy. It has been shown that the morphology of GaN layers strongly depends on the relative Ga-N bond concentration in the layers.

Control and near-field detection of surface plasmon interference patterns.

The tailoring of electromagnetic near-field properties is the central task in the field of nanophotonics. In addition to 2D optics for optical nanocircuits, confined and enhanced electric fields are utilized in detection and sensing, photovoltaics, spatially localized spectroscopy (nanoimaging), as well as in nanolithography and nanomanipulation. For practical purposes, it is necessary to develop easy-to-use methods for controlling the electromagnetic near-field distribution. By imaging optical near-fields using a scanning near-field optical microscope, we demonstrate that surface plasmon polaritons propagating from slits along the metal-dielectric interface form tunable interference patterns. We present a simple way how to control the resulting interference patterns both by variation of the angle between two slits and, for a fixed slit geometry, by a proper combination of laser beam polarization and inhomogeneous far-field illumination of the structure. Thus the modulation period of interference patterns has become adjustable and new variable patterns consisting of stripelike and dotlike motifs have been achieved, respectively.

An ultra-low energy (30-200 eV) ion-atomic beam source for ion-beam-assisted deposition in ultrahigh vacuum.

The paper describes the design and construction of an ion-atomic beam source with an optimized generation of ions for ion-beam-assisted deposition under ultrahigh vacuum (UHV) conditions. The source combines an effusion cell and an electron impact ion source and produces ion beams with ultra-low energies in the range from 30 eV to 200 eV. Decreasing ion beam energy to hyperthermal values (≈10(1) eV) without loosing optimum ionization conditions has been mainly achieved by the incorporation of an ionization chamber with a grid transparent enough for electron and ion beams. In this way the energy and current density of nitrogen ion beams in the order of 10(1) eV and 10(1) nA/cm(2), respectively, have been achieved. The source is capable of growing ultrathin layers or nanostructures at ultra-low energies with a growth rate of several MLs/h. The ion-atomic beam source will be preferentially applied for the synthesis of GaN under UHV conditions.