Jens Kling

In Situ Observations during Chemical Vapor Deposition of Hexagonal Boron Nitride on Polycrystalline Copper

Using a combination of complementary in situ X-ray photoelectron spectroscopy and X-ray diffraction, we study the fundamental mechanisms underlying the chemical vapor deposition (CVD) of hexagonal boron nitride (h-BN) on polycrystalline Cu. The nucleation and growth of h-BN layers is found to occur isothermally, i.e., at constant elevated temperature, on the Cu surface during exposure to borazine. A Cu lattice expansion during borazine exposure and B precipitation from Cu upon cooling highlight that B is incorporated into the Cu bulk, i.e., that growth is not just surface-mediated. On this basis we suggest that B is taken up in the Cu catalyst while N is not (by relative amounts), indicating element-specific feeding mechanisms including the bulk of the catalyst. We further show that oxygen intercalation readily occurs under as-grown h-BN during ambient air exposure, as is common in further processing, and that this negatively affects the stability of h-BN on the catalyst. For extended air exposure Cu oxidation is observed, and upon re-heating in vacuum an oxygen-mediated disintegration of the h-BN film via volatile boron oxides occurs. Importantly, this disintegration is catalyst mediated, i.e., occurs at the catalyst/h-BN interface and depends on the level of oxygen fed to this interface. In turn, however, deliberate feeding of oxygen during h-BN deposition can positively affect control over film morphology. We discuss the implications of these observations in the context of corrosion protection and relate them to challenges in process integration and heterostructure CVD.

Effect of uniaxial stress on ferroelectric behavior of (Bi1/2Na1/2)TiO3-based lead-free piezoelectric ceramics

Prior studies have shown that a field-induced ferroelectricity in ceramics with general chemical formula (1−x−y)(Bi1/2Na1/2)TiO3–xBaTiO3–y(K0.5Na0.5)NbO3 and a very low remanent strain can produce very large piezoelectric strains. Here we show that both the longitudinal and transverse strains gradually change with applied electric fields even during the transition from the nonferroelectric to the ferroelectric state, in contrast to known Pb-containing antiferroelectrics. Hence, the volume change and, in turn, the phase transition can be affected using uniaxial compressive stresses, and the effect on ferroelectricity can thus be assessed. It is found that the 0.94(Bi1/2Na1/2)TiO3–0.05BaTiO3–0.01(K0.5Na0.5)NbO3 ceramic (largely ferroelectric), with a rhombohedral R3c symmetry, displays large ferroelectric domains, significant ferroelastic deformation, and large remanent electrical polarizations even at a 250 MPa compressive stress. In comparison, the 0.91(Bi1/2Na1/2)TiO3–0.07BaTiO3–0.02(K0.5Na0.5)NbO3 ceram...

Organic light emitting diodes with environmentally and thermally stable doped graphene electrodes

We present a comparative study of the environmental and thermal stability of graphene charge transfer doping using molybdenum–trioxide (MoO3), vanadium–pentoxide (V2O5) and tungsten–trioxide (WO3). Our results show that all these metal oxides allow a strong and stable p-type doping of graphene, as well as functioning as effective hole-injection layers for highly efficient organic light emitting diodes.

Micro- and Nanostructural Characteristics of Particles Before and After an Exhaust Gas Recirculation System Scrubber

This work provides insight into the morphology and mixing state of submicron particles in diesel exhaust from a ship engine with an exhaust gas recirculation scrubber. Particles from this low-speed ship engine on test bed were collected using a microinertial impactor with transmission electron microscopy (TEM) grids on two stages. Micro- and nanostructural characteristics of single particles were studied by TEM. Image analysis was carried out on overview and high-resolution images, revealing influence of the exhaust gas treatment (scrubber) on the particle morphology and mixing state. Soot agglomerates were found to be collapsed after scrubber, reflected by their change in fractal dimension (Df ) from 1.88 to 2.13. Soot was predominantly found internally mixed with other components, with a higher degree of internal mixing observed after scrubber. Soot nanostructural characteristics on the near atomic scale such as layer distance, lamella length, and tortuosity were not observed to be influenced by the scrubber. We also found that particles in the size range between 30 and 50 nm, which were abundant in the exhaust before and after scrubber, were not graphitic soot. Furthermore, we found indications that these particles are composed of other crystalline material (salts). Copyright 2013 American Association for Aerosol Research

A-site occupancy in the lead-free (Bi1/2Na1/2TiO3)0.94-(BaTiO3)0.06 piezoceramic: Combining first-principles study and TEM

The crystal structure of the lead-free piezoelectric ceramic (Bi1/2Na1/2TiO3)0.94–(BaTiO3)0.06 was investigated by first-principles calculations and high-resolution transmission electron microscopy (HRTEM) imaging. Structures with different A-site occupation were relaxed by total energy calculations within density functional theory and then used for simulating the corresponding HRTEM images. Simulated and experimental HRTEM images were compared and the closest match selected for structure interpretation. By combining these techniques, we have identified the Bi(Ba)/Na distribution on the A-site to be homogeneous. We exclude the possibility that regions visible in HRTEM images within one grain can be attributed to different ordering but to a slight tilting of the structure with respect to the electron beam.

Growth Termination and Multiple Nucleation of Single-Wall Carbon Nanotubes Evidenced by in Situ Transmission Electron Microscopy

In order to controllably grow single-wall carbon nanotubes (SWCNTs), a better understanding of the growth processes and how they are influenced by external parameters such as catalyst and gaseous environment is required. Here, we present direct evidence of growth termination of individual SWCNTs and successive growth of additional SWCNTs on Co catalyst particles supported on MgO by means of environmental transmission electron microscopy. Such in situ observations reveal the plethora of solid carbon formations at the local scale while it is happening and thereby elucidate the multitude of configurations resulting from identical external synthesis conditions, which should be considered in the quest for controlled SWCNT growth. Using CO and a mixture of CO and H2 as carbon sources, we show that the growth of SWCNTs terminates with a reduced tube-catalyst adhesion strength. Two main reasons for the cessation are proposed: insufficient active carbon species and a certain amount of stress exerted at the tube-catalyst interface. Interestingly, it was observed that catalyst particles stayed active in terms of nucleating additional solid carbon structures after growth termination of the first SWCNT. These observations elucidate the importance of an in-depth understanding of the role of catalysts and carbon sources in the continued growth of SWCNTs. Furthermore, it serves as a guide for further control of carbon nanostructure synthesis via catalyst engineering and synthesis optimization.

Structure identification in high-resolution transmission electron microscopic images: an example on graphene.

A connection between microscopic structure and macroscopic properties is expected for almost all material systems. High-resolution transmission electron microscopy is a technique offering insight into the atomic structure, but the analysis of large image series can be time consuming. The present work describes a method to automatically estimate the atomic structure in two-dimensional materials. As an example graphene is chosen, in which the positions of the carbon atoms are reconstructed. Lattice parameters are extracted in the frequency domain and an initial atom positioning is estimated. Next, a plausible neighborhood structure is estimated. Finally, atom positions are adjusted by simulation of a Markov random field model, integrating image evidence and the strong geometric prior. A pristine sample with high regularity and a sample with an induced hole are analyzed. False discovery rate-controlled large-scale simultaneous hypothesis testing is used as a statistical framework for interpretation of results. The first sample yields, as expected, a homogeneous distribution of carbon-carbon (C-C) bond lengths. The second sample exhibits regions of shorter C-C bond lengths with a preferred orientation, suggesting either strain in the structure or a buckling of the graphene sheet. The precision of the method is demonstrated on simulated model structures and by its application to multiple exposures of the two graphene samples.

A Deep Learning Approach to Identify Local Structures in Atomic-Resolution Transmission Electron Microscopy Images

Recording atomic-resolution transmission electron microscopy (TEM) images is becoming increasingly routine. A new bottleneck is then analyzing this information, which often involves time-consuming manual structural identification. We have developed a deep learning-based algorithm for recognition of the local structure in TEM images, which is stable to microscope parameters and noise. The neural network is trained entirely from simulation but is capable of making reliable predictions on experimental images. We apply the method to single sheets of defected graphene, and to metallic nanoparticles on an oxide support.

Particle emission rates during electrostatic spray deposition of TiO2 nanoparticle-based photoactive coating

Here, we studied the particle release rate during Electrostatic spray deposition of anatase-(TiO2)-based photoactive coating onto tiles and wallpaper using a commercially available electrostatic spray device. Spraying was performed in a 20.3m3 test chamber while measuring concentrations of 5.6nm to 31μm-size particles and volatile organic compounds (VOC), as well as particle deposition onto room surfaces and on the spray gun user hand. The particle emission and deposition rates were quantified using aerosol mass balance modelling. The geometric mean particle number emission rate was 1.9×1010s-1 and the mean mass emission rate was 381μgs-1. The respirable mass emission-rate was 65% lower than observed for the entire measured size-range. The mass emission rates were linearly scalable (±ca. 20%) to the process duration. The particle deposition rates were up to 15h-1 for <1μm-size and the deposited particles consisted of mainly TiO2, TiO2 mixed with Cl and/or Ag, TiO2 particles coated with carbon, and Ag particles with size ranging from 60nm to ca. 5μm. As expected, no significant VOC emissions were observed as a result of spraying. Finally, we provide recommendations for exposure model parameterization.

Automated Structure Detection in HRTEM Images: An Example with Graphene

Graphene, as the forefather of 2D-materials, attracts much attention due to its extraordinary properties like transparency, flexibility and outstanding high conductivity, together with a thickness of only one atom. The properties seem to be dependent on the atomic structure of graphene and therefore characterizations on the atomic level are of interest. High-resolution transmission electron microscopy (HRTEM) is a state-of-the-art method to characterize the atomic structure of materials. Due to the inherently low mass-thickness of graphene, the contrast levels in the recorded images are often challenging to interpret. In order to increase the signal-to-noise ratio of the images two routes can be pursued: 1) the exposure time can be increased; or 2) acquiring series of images and summarize them after alignment. Both methods have the disadvantage of summing images acquired over a certain period of time making it difficult to resolve dynamic processes or unstable structures. Tools that assist to get the maximum of information out of recorded images are therefore greatly appreciated.