Thermally induced transformations of amorphous carbon nanostructures fabricated by electron beam induced deposition

We studied the thermally induced phase transformations of electron-beam-induced deposited (EBID) amorphous carbon nanostructures by correlating the changes in its morphology with internal microstructure by using combined atomic force microscopy (AFM) and high resolution confocal Raman microscopy. These carbon deposits can be used to create heterogeneous junctions in electronic devices commonly known as carbon-metal interconnects. We compared two basic shapes of EBID deposits: dots/pillars with widths from 50 to 600 nm and heights from 50 to 500 nm and lines with variable heights from 10 to 150 nm but having a constant length of 6 μm. We observed that during thermal annealing, the nanoscale amorphous deposits go through multistage transformation including dehydration and stress-relaxation around 150 °C, dehydrogenation within 150-300 °C, followed by graphitization (>350 °C) and formation of nanocrystalline, highly densified graphitic deposits around 450 °C. The later stage of transformation occurs well below commonly observed graphitization for bulk carbon (600-800 °C). It was observed that the shape of the deposits contribute significantly to the phase transformations. We suggested that this difference is controlled by different contributions from interfacial footprints area. Moreover, the rate of graphitization was different for deposits of different shapes with the lines showing a much stronger dependence of its structure on the density than the dots.     

Substrate atom enriched carbon nanostructures fabricated by focused electron beam induced deposition

Carbon nanostructures fabricated using focused electron beam induced deposition (FEBID) in a residual vacuum atmosphere or in the presence of low pressure precursor gas exhibit enrichment with the atoms of the substrate element. Nanostructures having base sizes up to 100?nm and height up to 250?nm with maximum substrate atom enrichment of 50% have been fabricated. The size of the structures (nanocones) and the substrate atom enrichment depends on the electron beam current density and irradiation time. A possible explanation of the phenomenon has been sought on the basis of local temperature rise and diffusion of the substrate atoms in the nanostructure during the growth process. The phenomenon can be used to fabricate dense 2D carbon nanopatterns enriched with a desired element used as the substrate material.     

Electron beam induced deposition of silicon nanostructures from a liquid phase precursor

This work demonstrates electron beam induced deposition of silicon from a SiCl(4) liquid precursor in a transmission electron microscope and a scanning electron microscope. Silicon nanodots of tunable size are reproducibly grown in controlled geometries. The volume of these features increases linearly with deposition time. The results indicate that secondary electrons generated at the substrate surface serve as the primary source of silicon reduction. However, at high current densities the influence of the primary electrons is observed to retard growth. The results demonstrate a new approach to fabricating silicon nanostructures and provide fundamental insights into the mechanism for liquid phase electron beam induced deposition.     

Focused electron beam induced etching of titanium with XeF2

Titanium is a relevant technological material due to its extraordinary mechanical and biocompatible properties, its nanopatterning being an increasingly important requirement in many applications. We report the successful nanopatterning of titanium by means of focused electron beam induced etching using XeF(2) as a precursor gas. Etch rates up to 1.25 × 10(-3) μm(3) s(-1) and minimum pattern sizes of 80 nm were obtained. Different etching parameters such as beam current, beam energy, dwell time and pixel spacing are systematically investigated, the etching process being optimized by decreasing both the beam current and the beam energy. The etching mechanism is investigated by transmission electron microscopy. Potential applications in nanotechnology are discussed.     

Fabrication of layered nanostructures by successive electron beam induced deposition with two precursors: protective capping of metallic iron structures

We report on the stepwise generation of layered nanostructures via electron beam induced deposition (EBID) using organometallic precursor molecules in ultra-high vacuum (UHV). In a first step a metallic iron line structure was produced using iron pentacarbonyl; in a second step this nanostructure was then locally capped with a 2-3 nm thin titanium oxide-containing film fabricated from titanium tetraisopropoxide. The chemical composition of the deposited layers was analyzed by spatially resolved Auger electron spectroscopy. With spatially resolved x-ray absorption spectroscopy at the Fe L? edge, it was demonstrated that the thin capping layer prevents the iron structure from oxidation upon exposure to air.     

Strategies for the immobilization of nanoparticles using electron beam induced deposition

The mechanism of electron-beam-induced immobilization of nanoparticles on a substrate has been studied both experimentally and theoretically. Experiments have been performed for the case of 200-350?nm Co-Ni nanoparticles secured to a substrate using a 30?keV electron beam. Atomic force microscopy studies reveal that the fixing occurs due to the formation of a deposit beneath the nanoparticles, causing strong bonding to the substrate, even for a thin layer. Measurements of the lateral forces required to displace the immobilized nanoparticles have shown that a deposit layer of 0.5?nm results in a tenfold increase in the bonding strength. A comparison of measured profiles with the results of computer simulations clearly reveals that the major role in the formation of the deposit is played by low-energy electrons generated by energetic primary electrons in both the nanoparticles and substrate. It is also shown that the efficiency of bonding decreases with decreasing energy of primary electrons. Different strategies for electron-beam-induced immobilization of nanoparticles and optimization of the processes are discussed.     

The influence of beam defocus on volume growth rates for electron beam induced platinum deposition

Electron beam induced deposition (EBID) is a versatile method for the controlled fabrication of conducting, semi-conducting and non-conducting structures down to the nanometer scale. In contrast to ion beam induced deposition, EBID processes are free of sputter effects, ion implantation and massive heat generation; however, they have much lower deposition rates. To push the deposition efficiency further towards its intrinsic limits, the individual influences of the process parameters have to be explored. In this work a platinum pre-cursor is used for the deposition of conducting nanorods on highly oriented pyrolytic graphite. The study shows the influence of a beam defocus during deposition on the volume growth rates. The temporal evolution of volume growth rates reveals a distinct maximum which is dependent on the defocus introduced, leading to an increase of deposited volumes by a factor 2.5 after the same deposition times. The observed maximum is explained by an increasing and saturating electron yield contributing to the final deposition process and constantly decreasing diffusion abilities of the pre-cursor molecules toward the tip of the nanorods, which is further supported by dwell time experiments.     

Focused electron beam induced deposition of gold catalyst templates for Si-nanowire synthesis

A new approach using focused electron beam induced deposition (FEBID) to deposit catalyst particles is reported for the synthesis of single crystalline silicon nanowires (SiNWs) grown by low pressure chemical vapor deposition (LPCVD). The FEBID deposited gold dot arrays fabricated from an acac-Au(III)-Me(2) precursor were investigated by AFM and EDX. The depositions were found to form a sharp tip and a surrounding halo and consist of only 10 at.% Au. However, SiNWs could be synthesized on the deposited catalyst using the vapor-liquid-solid (VLS) method with a mixture of 2% SiH(4) in He at 520?°C. NW diameters from 30 nm up to 150 nm were fabricated and the dependency of the NW diameter on the FEBID deposition time was observed. TEM analysis of the SiNWs revealed a [110] growth direction independent of the NW diameter. This new method provides a maskless and resistless approach for generating catalyst templates for SiNW synthesis on arbitrary surfaces.     

High spatial resolution imaging and spectroscopy in nanostructures

The challenge during the characterization of nanostructures is in extracting consistent local and spatially varying information from the structure and correlating it to the new physics that appears at the nanoscale. Recent years have seen exciting advances in imaging and spectroscopy techniques that can achieve this goal. The techniques offer the possibility to directly investigate local properties of materials with sub-nanometre spatial resolution. In this paper we review, from the perspective of our own contributions to the field of carbon nanostructures, recent advances in the application of nanoanalysis. Complementary techniques of spatially resolved electron, and scanning tunneling microscopy and spectroscopy, can be used to characterize and correlate the structure, topology, chemistry and electronic properties of nanostructures. Often the interpretation of the data needs to come from comparison with adequate theoretical models.     

Effects of electrons on the shape of nanopores prepared by focused electron beam induced etching

The fabrication of nanometric pores with controlled size is important for applications such as single molecule detection. We have recently suggested the use of focused electron beam induced etching (FEBIE) for the preparation of such nanopores in silicon nitride membranes. The use of a scanning probe microscope as the electron beam source makes this technique comparably accessible, opening the way to widespread fabrication of nanopores. Since the shape of the nanopores is critically important for their performance, in this work we focus on its analysis and study the dependence of the nanopore shape on the electron beam acceleration voltage. We show that the nanopore adopts a funnel-like shape, with a central pore penetrating the entire membrane, surrounded by an extended shallow-etched region at the top of the membrane. While the internal nanopore size was found to depend on the electron acceleration voltage, the nanopore edges extended beyond the primary electron beam spot size due to long-range effects, such as radiolysis and diffusion. Moreover, the size of the peripheral-etched region was found to be less dependent on the acceleration voltage. We also found that chemical etching is the rate-limiting step of the process and is only slightly dependent on the acceleration voltage. Furthermore, due to the chemical etch process the chemical composition of the nanopore rims was found to maintain the bulk membrane composition.     

High resolution electron tomography

Reaching atomic resolution in 3D has been the ultimate goal in the field of electron tomography for many years. Significant progress, both on the theoretical as well as the experimental side has recently resulted in several exciting examples demonstrating the ability to visualise atoms in 3D. In this paper, we will review the different steps that have pushed the resolution in 3D to the atomic level. A broad range of methodologies and practical examples together with their impact on materials science will be discussed. Finally, we will provide an outlook and will describe future challenges in the field of high resolution electron tomography.     

Ultrahigh resolution focused electron beam induced processing: the effect of substrate thickness

It is often suggested that the growth in focused electron beam induced processing (FEBIP) is caused not only by primary electrons, but also (and even predominantly) by secondary electrons (SEs). If that is true, the growth rate for FEBIP can be changed by modifying the SE yield. Results from our Monte Carlo simulations show that the SE yield changes strongly with substrate thickness for thicknesses below the SE escape depth. However, our experimental results show that the growth rate is independent of the substrate thickness. Deposits with an average size of about 3 nm were written on 1 and 9 nm thick carbon substrates. The apparent contradiction between simulation and experiment is explained by simulating the SE emission from a carbon substrate with platinum deposits on the surface. It appears that the SE emission is dominated by the deposits rather than the carbon substrate, even for deposits as small as 0.32 nm(3).     

Fabrication of nanostructures with different iron concentration by electron beam induced deposition with a mixture gas of iron carbonyl and ferrocene, and their magnetic properties

Electron beam induced deposition (EBID) with a mixture gas of iron carbonyl and ferrocene was carried out to fabricate nanostructures with different iron concentrations in a chamber of a scanning electron microscope. The iron concentration was controlled by changing the ratio of partial pressure of iron carbonyl and ferrocene. Electron holography observation revealed that the remanent magnetic flux density B _r values of the nanostructures were also changed depending on the iron concentration.     

Homogeneity of Ge-rich nanostructures as characterized by chemical etching and transmission electron microscopy

The extension of SiGe technology towards new electronic and optoelectronic applications on the Si platform requires that Ge-rich nanostructures be obtained in a well-controlled manner. Ge deposition on Si substrates usually creates SiGe nanostructures with relatively low and inhomogeneous Ge content. We have realized SiGe nanostructures with a very high (up to 90%) Ge content. Using substrate patterning, a regular array of nanostructures is obtained. We report that electron microscopy reveals an abrupt change in Ge content of about 20% between the filled pit and the island, which has not been observed in other Ge island systems. Dislocations are mainly found within the filled pit and only rarely in the island. Selective chemical etching and electron energy-loss spectroscopy reveal that the island itself is homogeneous. These Ge-rich islands are possible candidates for electronic applications requiring locally induced stress, and optoelectronic applications which exploit the Ge-like band structure of Ge-rich SiGe.     

CNT manipulation: inserting a carbonaceous dielectric layer beneath using electron beam induced deposition

Electron beam induced carbonaceous deposition has been carried out in the presence of water vapor at 0.4 torr pressure amidst residual hydrocarbons present in the SEM chamber. When performed at a CNT location on a Si substrate with low e beam energy (10 kV), the deposition was taking place beneath the CNT. While higher beam energy (25 kV) causing the deposition on the top surface of the CNT, in agreement with the earlier reports. The insertion of dielectric carbonaceous layer beneath the CNT allowed us to measure the I-V data along the length of the nanotube using CAFM.     

Oriented carbon nanostructures containing nitrogen obtained by ion beam assisted deposition

In this paper, we report the deposition of graphite multilayer containing nitrogen covering nanometric nickel particles. In-situ photoelectron emission spectroscopy (XPS) reveals the presence of nitrogen in the carbon layer covering the nickel particles. The field emission properties of the structures are reported. Atomic force microscopy displays regular domelike structures. Raman spectroscopy shows the characteristic frequencies associated with graphite and disordered structures. High-resolution transmission electron microscopy confirms the presence of multiwall well-organized graphite layers covering the nickel particles. Disorder increases on increasing nitrogen content. The samples were prepared in-situ by depositing first a few atomic layers of nickel and subsequent islands formation by thermal annealing. Then, an argon ion beam bombards an ultrapure carbon target and simultaneously the growing film is assisted with a second low-energy nitrogen ion beam (ion beam assisted deposition).     

Nanosynthesis of tunable composite materials by room-temperature pulsed focused electron beam induced chemical vapour deposition

Hydrocarbons inherently present in standard high-vacuum scanning electron microscopes can be favorably used for co-deposition with functional molecules injected into the chamber. By varying the beam exposure pulse time the carbon content incorporated into the deposit can be tuned. In the particular case when the hydrocarbons are provided by surface diffusion, the composition depends also on the size of the final deposits. This dependency can be used as an additional parameter, besides the beam pulse time, in order to tune the metal/matrix ratio and to obtain new nanoscale materials with tailored physical properties. We present and discuss experimental results on composition tunability by pulsed electron-beam deposition for the two-adsorbate system Co2(CO)8/hydrocarbon and their use in fabricating Hall nanosensors of cobalt-carbon nanocomposite material with enhanced magnetic sensitivity and high magnetic spatial resolution.     

Nanoscale electron beam induced etching: a continuum model that correlates the etch profile to the experimental parameters

In this paper, we relate experimental electron beam induced etching profiles to various electron limited and mass transport limited regimes via a continuum model. In particular, we develop a series of models with increasing complexity and demonstrate the effects and interactions that the precursor gas adsorption kinetics, the electron flux distribution, and the etch product desorption kinetics have on the resultant nanoscale etching profile. Unlike analogous electron beam induced deposition models, it is shown that one must consider the diffusion, desorption, and possible re-dissociation of the resultant etch product to understand the observed etching profiles. To confirm the explanation of the etch results, a defocus experiment was performed showing transitions from the electron flux limited to the mass transport limited to the etch product dissociation limited regimes.     

High resolution electron microscopy of superconductors

Until recently, in the field of superconductivity, electron microscopy has played only a minor role in studies of structure and properties of existing superconductors (except Nb and its alloys) and in the development of new and improved superconductors. This situation has changed in recent years. Electron microscopy is now being extensively used to study the growth, microstructure, and kinetics of many superconductors, especially of A15 type. Electron microscopy has also contributed to the understanding of the nature of radiation damage in these materials. These contributions will be reviewed with selected examples.     

High resolution electron microscopy of alloys

High resolution electron microscopy (HREM) has emerged as a very powerful tool for probing the structure of metals and alloys. It has not only helped in unravelling the structure of materials which have been at the forefront of novel materials development such as quasicrystalline phases and high temperature superconducting compounds, but also is fast becoming a technique for solving some outstanding issues in the case of the commercial alloys thereby helping alloy development. In addition to the determination of the structures of phases, this tool is used for obtaining a first hand information of the arrangement of atoms around the various types of crystallographic defects and interphase interfaces. This mode of microscopy allows direct observation of orientation relationships between two phases across interfaces. HREM can be used for the direct examination of the prenucleation process. Initial stages of nucleation can also be studied readily in amorphous alloys, precipitation hardening alloys like maraging steels and in those systems where the formation of the omega phase occurs. This presentation describes some results of HREM studies on various alloys, commercial as well as alloys of scientific interest, where some of the aforementioned aspects have been examined. The specific examples cited pertain to metallic glasses, NiTi shape memory alloys, Ni-Mo, Zr-Nb and Ti-Al alloys.