Shaping the lens of the atom probe: fabrication of site specific, oriented specimens and application to grain boundary analysis

The random sampling provided by classical atom probe sample preparation methods is one of the major factors limiting the types of problems that can be addressed using this powerful technique. A focused ion beam enables not only site-specific preparation, but can also be used to give the specimen, which acts as the lens in an atom probe experiment, a specific shape. In this paper we present a technique that uses low accelerating voltages (10 and 5 kV) in the focused ion beam (FIB) to reproducibly produce specimens with selected grain boundaries <100 nm from the tip at any desired orientation. These tips have a high rate of successfully running in the atom probe and no Ga contamination within the region of interest.This technique is applied to the analysis of grain boundaries in a high purity iron wire and a strip-cast steel. Lattice resolution is achieved around the boundary in certain areas. Reconstruction of these datasets reveals the distribution of light and heavy elements around the boundary. Issues surrounding the uneven distribution of certain solute elements as a result of field-induced diffusion are discussed.     

Broadening the applications of the atom probe technique by ultraviolet femtosecond laser

Laser assisted field evaporation using ultraviolet (UV) wavelength gives rise to better mass resolution and signal-to-noise ratio in atom probe mass spectra of metals, semiconductors and insulators compared to infrared and green lasers. Combined with the site specific specimen preparation techniques using the lift-out and annular Ga ion milling in a focused ion beam machine, a wide variety of materials including insulating oxides can be quantitatively analyzed by the three-dimensional atom probe using UV laser assisted field evaporation. After discussing laser irradiation conditions for optimized atom probe analyses, recent atom probe tomography results on oxides, semiconductor devices and grain boundaries of sintered magnets are presented.     

Atom probe trajectory mapping using experimental tip shape measurements

Atom probe tomography is an accurate analytical and imaging technique which can reconstruct the complex structure and composition of a specimen in three dimensions. Despite providing locally high spatial resolution, atom probe tomography suffers from global distortions due to a complex projection function between the specimen and detector which is different for each experiment and can change during a single run. To aid characterization of this projection function, this work demonstrates a method for the reverse projection of ions from an arbitrary projection surface in 3D space back to an atom probe tomography specimen surface. Experimental data from transmission electron microscopy tilt tomography are combined with point cloud surface reconstruction algorithms and finite element modelling to generate a mapping back to the original tip surface in a physically and experimentally motivated manner. As a case study, aluminium tips are imaged using transmission electron microscopy before and after atom probe tomography, and the specimen profiles used as input in surface reconstruction methods. This reconstruction method is a general procedure that can be used to generate mappings between a selected surface and a known tip shape using numerical solutions to the electrostatic equation, with quantitative solutions to the projection problem readily achievable in tens of minutes on a contemporary workstation.     

基于SPM的纳米加工技术研究进展

扫描探针显微镜(SPM)使人们不仅可以观察到物质表面的微观形貌,还可以在微纳米尺度上对样品表面进行加工,这种方法有可能成为未来微纳米器件的主要制作方法,成为推动人类科学和技术发展的新动力。主要介绍基于SPM的三种纳米加工方法:单原子操纵法、阳极氧化法和机械刻蚀法。详细阐述了各自的原理、特点及发展状况,并指出阳极氧化法是目前最有可能应用在实际生产制造中的加工方法,而机械刻蚀法则不仅可以作为纳米加工的手段,还可以应用于纳米加工机理方面的研究。     

扫描离子电导显微镜技术及其在纳米生物学研究中的应用

扫描探针显微镜技术的出现开辟生命科学研究的新纪元并逐步发展成为在纳米尺度研究细胞结构与功能的一类新型的显微镜技术。扫描离子电导显微镜技术就是新近发展起来的这一扫描探针显微镜技术家族中的一员,可被用来在生理条件下、高分辨率及非接触地研究活细胞的表面形貌,从而帮助人们深入研究细胞微观结构与功能的关系。本文简要介绍扫描离子电导显微镜技术的基本原理,并结合国外研究现状综述该技术在纳米生物学研究中的应用。     

Contingency table techniques for three dimensional atom probe tomography

A contingency table analysis procedure is developed and applied to three dimensional atom probe data sets for the investigation of fine-scale solute co-/anti-segregation effects in multicomponent alloys. Potential sources of error and inaccuracy are identified and eliminated from the technique. The conventional P value testing techniques associated with chi(2) are shown to be unsatisfactory and can become ambiguous in cases of large block numbers or high solute concentrations. The coefficient of contingency is demonstrated to be an acceptable and useful basis of comparison for contingency table analyses of differently-conditioned materials. However, care must be taken in choice of block size and to maintain a consistent overall composition between experiments. The coefficient is dependent upon block size and solute composition, and cannot be used to compare analyses with significantly different solute compositions or to assess the extent of clustering without reference to that of the randomly ordered case. It is shown that as clustering evolves into larger precipitates and phases, contingency table analysis becomes inappropriate. Random labeling techniques are introduced to infer further meaning from the coefficient of contingency. We propose the comparison of experimental result, mu(exp), to the randomized value, micro(rand), as a new method by which to interpret the quantity of solute clustering present in a material. It is demonstrated that how this method may be utilized to identify an appropriate size of contingency table analysis blocks into which the data set is partitioned to optimize the significance of the results.     

Estimating the physical cluster‐size distribution within materials using atom‐probe

A limiting characteristic of the atom‐probe technique is the nondetection of ions and this embodies a significant “missing information” problem in investigations of atomic clustering phenomena causing difficulty in the interpretation of any atom‐probe experiment. It is shown that the measurable cluster‐size distribution can be modeled by a mixed binomial distribution. A deconvolution method based upon expectation‐maximization (EM) algorithm is presented to obtain the original physical distribution from an efficiency‐degraded distribution, thereby providing means to calculate accurate cluster number densities from atom probe results. The accuracy of this restoration was predominantly dependent upon the detector efficiency and was proved to be highly accurate in the case of conventional atom‐probe detector efficiencies (? = 57%). Such considerations and measures are absolutely necessary when the number density of clusters and small precipitates is in any way regarded as important. We conclude that limitations in detector efficiency are more limiting for cluster‐finding analyses via atom‐probe techniques than spatial resolution issues, and therefore the current endeavors for improving detector technologies are well found. Microsc. Res. Tech., 2011. © 2010 Wiley‐Liss, Inc.     

3-D analysis of semiconductor dopant distributions in a patterned structure using LEAP

This work presents the first 3-D analysis of lateral dopant diffusion in a patterned structure using a pulsed laser-assisted local electrode atom probe (LEAP). A structure similar to a device channel was created for this work by performing a 3 keV, 1×10¹⁵ cm⁻² As⁺ implant on a poly-Si line patterned wafer with 70 nm line width and 200 nm line pitch. The wafer was subsequently annealed at 950 °C for 1 s. LEAP samples were made using a site-selective in-situ focused ion beam (FIB) process. The results from LEAP analysis were then compared with high-resolution transmission electron microscopy (HRTEM) and Florida object-oriented process simulator (FLOOPS) results. Good structural agreement was found between the LEAP and HRTEM results. Several 1-D As concentration profiles extracted from the LEAP data were also found to be in good agreement with FLOOPS process simulation results. These profiles also represent for the first time that results from a 3-D process simulator have been able to be confirmed experimentally using a single sample.     

Multi-objective optimal design of high frequency probe for scanning ion conductance microscopy

Scanning ion conductance microscopy(SICM) is an emerging non-destructive surface topography characterization apparatus with nanoscale resolution. However, the low regulating frequency of probe in most existing modulated current based SICM systems increases the system noise, and has difficulty in imaging sample surface with steep height changes. In order to enable SICM to have the capability of imaging surfaces with steep height changes, a novel probe that can be used in the modulated current based hopping mode is designed. The design relies on two piezoelectric ceramics with different travels to separate position adjustment and probe frequency regulation in the Z direction. To further improve the resonant frequency of the probe, the material and the key dimensions for each component of the probe are optimized based on the multi-objective optimization method and the finite element analysis. The optimal design has a resonant frequency of above 10 kHz. To validate the rationality of the designed probe, microstructured grating samples are imaged using the homebuilt modulated current based SICM system. The experimental results indicate that the designed high frequency probe can effectively reduce the spike noise by 26% in the average number of spike noise. The proposed design provides a feasible solution for improving the imaging quality of the existing SICM systems which normally use ordinary probes with relatively low regulating frequency.     

Microstructural investigation of Sr-modified Al-15 wt%Si alloys in the range from micrometer to atomic scale

Strontium-modified Al-15 wt%Si casting alloys were investigated after 5 and 60 min of melt holding. The eutectic microstructures were studied using complementary methods at different length scales: focused ion beam-energy selective backscattered tomography, transmission electron microscopy and 3D atom probe. Whereas the samples after 5 min of melt holding show that the structure of eutectic Si changes into a fine fibrous morphology, the increase of prolonged melt holding (60 min) leads to the loss of Sr within the alloy with an evolution of an unmodified eutectic microstructure displaying coarse interconnected Si plates. Strontium was found at the Al/Si eutectic interfaces on the side of the eutectic Al region, measured by 3D atom probe. The new results obtained using 3D atom probe shed light on the location of Sr within the Al-Si eutectic microstructure.     

The influence of oxide surface layers on bulk electron probe microanalysis of oxygen—application to Ti-Si-O compounds

This paper discusses a generalized method to measure with the electron probe microanalyzer (EPMA) the oxygen in a material containing a surface oxide layer. The continuum background is the most difficult to measure, particularly for materials in which oxygen-free samples cannot be produced. The method depends on the preparation of either oxygen-free samples or well characterized oxygen-containing samples. Specific application of the method to the Ti-Si-O system is discussed. In addition, measurements of oxide surface-layer thickness of 3.6–8.0 nm on Ti and Ti-Si compounds were obtained using EPMA and a scanning Auger microprobe (SAM). The nature of the oxide surface layers was shown using x-ray photoelectron spectroscopy (XPS).     

Optimisation of four-sensor probes for measuring bubble velocity components in bubbly air-water and oil-water flows

In a previous paper Lucas and Mishra (2005) [3] a local four-sensor conductance probe was introduced to measure the velocity vectors of dispersed bubbles in bubbly two-phase flow in which the continuous phase is water. There are a very limited number of alternative methods available for bubble velocity vector measurement with which results from, for example, computational fluid dynamic models can be compared and so the four-sensor probe technique is of interest to the multiphase flow community. In the previous paper [3] a mathematical model was presented to calculate the velocity vector of each gas bubble from seven time intervals which were measured using the output signals from each of four ‘needle’ conductance sensors located within the probe. In the present paper, a new technique for making the local four-sensor probe is introduced to minimise interference with the measured bubbles. A new signal processing method is presented using criteria to ensure that (i) the group of sensor signals from which the bubble velocity vector is to be determined are all produced by the same bubble and (ii) bubbles which contact the local four-sensor probe in an ambiguous manner are ignored. The accuracy with which the locations of each of the rear sensors in the probe relative to the lead sensor can be measured influences the accuracy with which the bubble velocity vector can be measured. However, the degree to which the accuracy of the measured velocity vector is affected by errors in the measured probe dimensions is dependent upon the geometrical arrangement of the four sensors within the probe. Experimental results and an error analysis are presented which show that the susceptibility of the velocity vector measurement technique to errors in the measured probe dimensions is reduced if the geometrical arrangement of the four sensors is optimised. As a result of this initial work, an optimised probe, known as the P30 probe, was designed and built and results obtained from the P30 probe in swirling oil-in-water bubbly flow are presented. A probe calibration factor is defined in this paper which can be interpreted as a measure of the interference of a probe with the motion of the bubbles with which it interacts. For the probes described in this paper the calibration factor was found to be much closer to unity than for previous four-sensor probes described in the literature (e.g. [3]) suggesting that these new probes have a much smaller effect on the bubbles’ motion than previous probes.     

Investigations of field-evaporated end forms in voltage- and laser-pulsed atom probe tomography

Atom Probe Tomography (APT) consists of analyzing a needle-shaped specimen on an atom-by-atom basis. In recent years, instruments have become commercially available, enabling the sequential analysis of the same specimen in both laser- and voltage-pulsed modes. In this contribution, a comparison of field evaporated end-forms as a function of the voltage and laser power is presented for silicon. Electron microscopy is utilized for visual inspection of the final tip end-forms. The field of evaporation for silicon is calculated based on these radius measurements for voltage and laser pulsing. Electron microscopy and analysis of the atom probe data show that the specimen end-forms for both pulsing modes can be different. We have observed two effects on the shape of a field-ion emitter when irradiated by a focused laser beam. One is a change in the 3-dimensional topology of the emitter due to different crystallographic orientations. Secondly, exposure to focused laser beam from one side may lead to a non-hemispherical tip shape especially when reasonably high laser energy is utilized. For comparison purposes to the laser mode, the voltage pulse evaporated tip end form is also analyzed for different specimen temperatures. Consequently, evaporation fields are calculated for different temperatures and laser conditions for silicon.     

Determination of matrix composition based on solute‐solute nearest‐neighbor distances in atom probe tomography

In this study, we propose a fast automatic method providing the matrix concentration in an atom probe tomography (APT) data set containing two phases or more. The principle of this method relies on the calculation of the relative amount of isolated solute atoms (i.e., not surrounded by a similar solute atom) as a function of a distance d in the APT reconstruction. Simulated data sets have been generated to test the robustness of this new tool and demonstrate that rapid and reproducible results can be obtained without the need of any user input parameter. The method has then been successfully applied to a ternary Al‐Zn‐Mg alloy containing a fine dispersion of hardening precipitates. The relevance of this method for direct estimation of matrix concentration is discussed and compared with the existing methodologies. Microsc. Res. Tech., 2010. © 2010 Wiley‐Liss, Inc.     

Cleaning AFM colloidal probes by mechanically scrubbing with supersharp “brushes”

Contamination control of atomic force microscope (AFM) tips (including standard but supersharp imaging tips and particle/colloidal probes) is very important for reliable AFM imaging and surface/interface force measurements. Traditional cleaning methods such as plasma, UV–ozone and solvent treatments have their shortcomings. Here, we demonstrate that calibration gratings with supersharp spikes can be employed to scrub away contaminants accumulated on a colloidal sphere probe by scanning the probe against the spikes at high load at constant-force mode. The present method is superior to traditional cleaning methods in several aspects. First, accumulated lump-like organic/inorganic material can be removed; second, removal is non-destructive and highly efficient based on a “targeted removal” strategy; third, removal and probe shape/morphology study can be completed in a single step (we report, to our best knowledge, the first evidence of the wear of the colloidal sphere during force measurements); and fourth, both colloidal/particle probes and standard but supersharp AFM imaging tips can be treated.     

用于工业三维点测量的接触式光学探针

为了快速、准确地获得大尺寸工业产品或带有深槽孔工件的关键点三维坐标,本文基于工业近景摄影测量理论、立体视觉技术等,研究并实现了两种工业便携式、接触式光学探针测量系统。研究了测量系统涉及的探针设计、探针标定以及三维点解算等关键技术,设计了点阵式和手持相机式两种适用于不同工业场合的工业探针。针对点阵式探针的测量,提出了一种用于解算探针坐标系与世界坐标系相对关系的点云匹配方法。此外,采用拟合虚拟球的方法准确标定了两种探针的内部参数。最后,通过对比标准球与三坐标测量机的测量结果,得到系统的测量精度可达0.1 mm/m。该精度满足一般大、中型工件的三维点测量精度标准。     

Modelling of pretravel for touch trigger probes on indexable probe heads on coordinate measuring machines

This paper presents a pretravel model for touch trigger probes mounted on indexable probe heads, which can rotate and tilt the probe into a number of orientations for coordinate measurements on coordinate measuring machines (CMMs). Pretravel accounts for the majority of touch trigger probe errors and is caused by bending deflection of the stylus shaft. A trigger force model is derived and used to model bending deflection of the stylus shaft at the trigger instant. Only one model parameter needs to be calculated using the probe calibration data. Experimental data associated with thirteen probe orientations were used to validate the model. It is shown that the model can effectively predict pretravel distances associated with various probe approach directions. The standard deviations of prediction errors are less than 0.71 µm, indicating that the proposed model can be used to compensate for pretravels occurring in touch trigger probe applications.     

Quantitative X-ray analysis of biological fluids: The microdroplet technique

X-ray microanalysis can be used to quantitatively determine the elemental composition of microvolumes of biological fluids. This article describes the various steps in preparation of microdroplets for analysis: The manufacturing of micropipettes, the preparation of the specimen support, the deposition of droplets on the support, shock-freezing, and lyophilization. Examples of common artifacts (incomplete rehydration prior to freezing or partial rehydration after lyophilization) are demonstrated. Analysis can be carried out either by wavelength-dispersive analysis, which is the most sensitive method, or by energy-dispersive analysis, which is more commonly available. The mininum detectable concentration is 0.05 mmol · liter^?1 for 0.1-nl samples analyzed by wavelength-dispersive spectrometry and 0.5–1 mmol · liter^?1 for samples analyzed by energy-dispersive spectrometry. A major problem, especially in wavelength-dispersive analysis, where high beam currents are used, is radiation damage to the specimen; in particular chloride (but also other elements) can be lost. Quantitative analysis requires the use of standard solutions with elemental concentration in the same range as those present in the specimen.     

Gallium-enhanced phase contrast in atom probe tomography of nanocrystalline and amorphous Al-Mn alloys

Over a narrow range of composition, electrodeposited Al-Mn alloys transition from a nanocrystalline structure to an amorphous one, passing through an intermediate dual-phase nanocrystal/amorphous structure. Although the structural change is significant, the chemical difference between the phases is subtle. In this study, the solute distribution in these alloys is revealed by developing a method to enhance phase contrast in atom probe tomography (APT). Standard APT data analysis techniques show that Mn distributes uniformly in single phase (nanocrystalline or amorphous) specimens, and despite some slight deviations from randomness, standard methods reveal no convincing evidence of Mn segregation in dual-phase samples either. However, implanted Ga ions deposited during sample preparation by focused ion-beam milling are found to act as chemical markers that preferentially occupy the amorphous phase. This additional information permits more robust identification of the phases and measurement of their compositions. As a result, a weak partitioning tendency of Mn into the amorphous phase (about 2 at%) is discerned in these alloys.     

Fabrication and characterization of APT specimens from high dose heavy ion irradiated materials

The next generations of advanced energy systems will require materials that can withstand high doses of irradiation at elevated temperatures. Therefore, a methodology has been developed for the fabrication of high-dose ion-irradiated atom probe tomography specimens at a specific dose with the use of a focused ion beam milling system. The method also enables the precise ion dose of the atom probe tomography specimen to be estimated from the local concentration of the implanted ions. The method has been successfully applied to the characterization of the distribution of nanoclusters in a radiation-tolerant 14YWT nanostructured ferritic steel under ion irradiation to doses up to 400 displacements per atom.