Fluctuation Electron Microscopy on Amorphous Silicon and Amorphous Germanium.

Variable resolution fluctuation electron microscopy experiments were performed on self-ion implanted amorphous silicon and amorphous germanium to analyze the medium-range order. The results highlight that the commonly used pair-persistence analysis is influenced by the experimental conditions. Precisely, the structural correlation length Λ, a metric for the medium-range order length scale in the material, obtained from this particular evaluation varies depending on whether energy filtering is used to acquire the data. In addition, Λ depends on the sample thickness. Both observations can be explained by the fact that the pair-persistence analysis utilizes the experimentally susceptible absolute value of the normalized variance obtained from fluctuation electron microscopy data. Instead, plotting the normalized variance peak magnitude over the electron beam size offers more robust results. This evaluation yields medium-range order with an extent of approximately (1.50 ± 0.50) nm for the analyzed amorphous germanium and around (1.10 ± 0.20) nm for amorphous silicon.

Challenges of Electron Correlation Microscopy on Amorphous Silicon and Amorphous Germanium.

Electron correlation microscopy experiments were conducted on amorphous germanium (a-Ge) and amorphous silicon (a-Si) with the goal to study self-diffusion. For this purpose, a series of tilted dark-field images were acquired during in situ heating of the samples in a transmission electron microscope. These experiments show that the measurements are greatly affected by artefacts. Contamination, crystallization, electron beam-induced sputtering, and macroscopic bending of the samples pose major obstacles to the measurements. Other, more subtle experimental artefacts could occur in addition to these which makes interpretations regarding the structural dynamics nearly impossible. The data were nonetheless evaluated to see if some useful information could be extracted. One such result is that the distribution of the characteristic times τKWW, which were obtained from stretched exponential fits to the intensity autocorrelation data, is spatially heterogeneous. This spatial heterogeneity is assumed to be caused by a potential nonergodicity of the materials, the artefacts or an inhomogeneous amorphous structure. Further data processing shows that the characteristic times τKWW are moreover temperature independent, especially for the a-Ge data. It is concluded that the structural rearrangements over time are primarily electron beam-driven and that diffusive dynamics are too slow to be measured at the chosen, experimentally accessible annealing temperatures.

Treating Knock-On Displacements in Fluctuation Electron Microscopy Experiments.

This work investigates how knock-on displacements influence fluctuation electron microscopy (FEM) experiments. FEM experiments were conducted on amorphous silicon, formed by self-ion implantation, in a transmission electron microscope at 300 kV and 60 kV at various electron doses, two different binnings and with two different cameras, a CCD and a CMOS one. Furthermore, energy filtering has been utilized in one case. Energy filtering greatly enhances the FEM data by removing the inelastic background intensity, leading to an improved speckle contrast. The CMOS camera yields a slightly larger normalized variance than the CCD at an identical electron dose and appears more prone to noise at low electron counts. Beam-induced atomic displacements affect the 300 kV FEM data, leading to a continuous suppression of the normalized variance with increasing electron dose. Such displacements are considerably reduced for 60 kV experiments since the primary electron's maximum energy transfer to an atom is less than the displacement threshold energy of amorphous silicon. The results show that the variance suppression due to knock-on displacements can be controlled in two ways: Either by minimizing the electron dose to the sample or by conducting the experiment at a lower acceleration voltage.

Focused Ion Beam Sample Preparation for In Situ Thermal and Electrical Transmission Electron Microscopy.

A focused ion beam (FIB) technique describing the preparation of specimens for in situ thermal and electrical transmission electron microscopy is presented in detail. The method can be applied to a wide range of materials and allows the sample to be thinned down to electron transparency while it is attached to the in situ chip. This offers the advantage that the specimen can have a quality in terms of contamination and damage due to the ion beam that is comparable to samples prepared by means of conventional FIB preparation. Additionally, our technique can be performed by most commercially available FIB devices and only requires three simple, custom stubs for the procedure. This should enable a large userbase for this type of sample fabrication. One further benefit of our technique is that the in situ chip can be reused to create another sample on the same chip. The quality of the samples is demonstrated by high-resolution transmission electron microscopy as well as electron energy loss spectroscopy.

Comparison of Experimental STEM Conditions for Fluctuation Electron Microscopy.

Variable-resolution fluctuation electron microscopy (VR-FEM) data from measurements on amorphous silicon and PdNiP have been obtained at varying experimental conditions. Measurements have been conducted at identical total electron dose and with an identical electron dose normalized to the respective probe size. STEM probes of different sizes have been created by variation of the semi-convergence angle or by defocus. The results show that defocus yields a reduced normalized variance compared to data from probes created by convergence angle variation. Moreover, the trend of the normalized variance upon probe size variation differs between the two methods. Beam coherence, which affects FEM data, has been analyzed theoretically using geometrical optics on a multi-lens setup and linked to the illumination conditions. Fits to several experimental beam profiles support our geometrical optics theory regarding probe coherence. The normalized variance can be further optimized if one determines the optimal exposure time for the nanobeam diffraction patterns.

Electrochemical Proton Intercalation in Vanadium Pentoxide Thin Films and its Electrochromic Behavior in the near-IR Region.

This work examines the proton intercalation in vanadium pentoxide (V2 O5 ) thin films and its optical properties in the near-infrared (near-IR) region. Samples were prepared via direct current magnetron sputter deposition and cyclic voltammetry was used to characterize the insertion and extraction behavior of protons in V2 O5 in a trifluoroacetic acid containing electrolyte. With the same setup chronopotentiometry was done to intercalate a well-defined number of protons in the Hx V2 O5 system in the range of x=0 and x=1. These films were characterized with optical reflectometry in the near-IR region (between 700 and 1700 nm wavelength) and the refractive index n and extinction coefficient k were determined using Cauchy's dispersion model. The results show a clear correlation between proton concentration and n and k.

Structural and Thermal Characterisation of Nanofilms by Time-Resolved X-ray Scattering.

High time resolution in scattering analysis of thin films allows for determination of thermal conductivity by transient pump-probe detection of dissipation of laser-induced heating, TDXTS. We describe an approach that analyses the picosecond-resolved lattice parameter reaction of a gold transducer layer on pulsed laser heating to determine the thermal conductivity of layered structures below the transducer. A detailed modeling of the cooling kinetics by a Laplace-domain approach allows for discerning effects of conductivity and thermal interface resistance as well as basic depth information. The thermal expansion of the clamped gold film can be calibrated to absolute temperature change and effects of plastic deformation are discriminated. The method is demonstrated on two extreme examples of phononic barriers, isotopically modulated silicon multilayers with very small acoustic impedance mismatch and silicon-molybdenum multilayers, which show a high resistivity.

Ion-Beam-Induced Atomic Mixing in Ge, Si, and SiGe, Studied by Means of Isotope Multilayer Structures.

Crystalline and preamorphized isotope multilayers are utilized to investigate the dependence of ion beam mixing in silicon (Si), germanium (Ge), and silicon germanium (SiGe) on the atomic structure of the sample, temperature, ion flux, and electrical doping by the implanted ions. The magnitude of mixing is determined by secondary ion mass spectrometry. Rutherford backscattering spectrometry in channeling geometry, Raman spectroscopy, and transmission electron microscopy provide information about the structural state after ion irradiation. Different temperature regimes with characteristic mixing properties are identified. A disparity in atomic mixing of Si and Ge becomes evident while SiGe shows an intermediate behavior. Overall, atomic mixing increases with temperature, and it is stronger in the amorphous than in the crystalline state. Ion-beam-induced mixing in Ge shows no dependence on doping by the implanted ions. In contrast, a doping effect is found in Si at higher temperature. Molecular dynamics simulations clearly show that ion beam mixing in Ge is mainly determined by the thermal spike mechanism. In the case of Si thermal spike, mixing prevails at low temperature whereas ion beam-induced enhanced self-diffusion dominates the atomic mixing at high temperature. The latter process is attributed to highly mobile Si di-interstitials formed under irradiation and during damage annealing.

Time-domain electrostatic force spectroscopy on nanostructured lithium-ion conducting glass ceramics: analysis and interpretation of relaxation times.

The nanoscopic electrical properties of LiAlSiO(4) glass ceramics with different degrees of crystallinity chi were studied by means of time-domain electrostatic force spectroscopy (TDEFS). Thereby, a faster relaxation process due to lithium ion movements in the glassy phase and a slower process due to lithium ion movements in the crystallites could be distinguished. Over a broad range of crystallinity values, the TDEFS relaxation times of both processes are Arrhenius activated, with an activation energy being essentially independent of chi and with a pre-exponential factor depending in a systematic fashion on chi. With increasing crystallinity, the pre-exponential factor of the faster process (glassy phase) increases, while that of the slower process (crystallites) decreases. In order to explain this observation, we consider simple equivalent circuit models for the capacitance relaxation of the system AFM tip/gap/sample.

Fast interfacial ionic conduction in nanostructured glass ceramics.

The hopping movements of mobile ions in a nanostructured LiAlSiO4 glass ceramic are characterized by time-domain electrostatic force spectroscopy (TDEFS). While the macroscopic conductivity spectra are governed by a single activation energy, the nanoscopic TDEFS measurements reveal three different dynamic processes with distinct activation energies. Apart from the ion transport processes in the glassy and crystalline phases, we identify a third process with a very low activation energy, which is assigned to ionic movements at the interfaces between the crystallites and glassy phase. Such interfacial processes are believed to play a key role for obtaining high ionic conductivities in nanostructured solid electrolytes.

Nanoscopic study of the ion dynamics in a LiAlSiO4 glass ceramic by means of electrostatic force spectroscopy.

We use time-domain electrostatic force spectroscopy (TD-EFS) for characterising the dynamics of mobile ions in a partially crystallised LiAlSiO4 glass ceramic, and we compare the results of the TD-EFS measurements to macroscopic electrical conductivity measurements. While the macroscopic conductivity spectra are determined by a single dynamic process with an activation energy of 0.72 eV, the TD-EFS measurements provide information about two distinct relaxation processes with different activation energies. Our results indicate that the faster process is due to ionic movements in the glassy phase and at the glass-crystal interfaces, while the slower process is caused by ionic movements in the crystallites. The spatially varying electrical relaxation strengths of the fast and of the slow process provide information about the nano- and mesostructure of the glass ceramic.