Laser-assisted Atom Probe Research Articles

Field-Dependent Measurement of GaAs Composition by Atom Probe Tomography.

The composition of GaAs measured by laser-assisted atom probe tomography may be inaccurate depending on the experimental conditions. In this work, we assess the role of the DC field and the impinging laser energy on such compositional bias. The DC field is found to have a major influence, while the laser energy has a weaker one within the range of parameters explored. The atomic fraction of Ga may vary from 0.55 at low-field conditions to 0.35 at high field. These results have been interpreted in terms of preferential evaporation of Ga at high field. The deficit of As is most likely explained by the formation of neutral As complexes either by direct ejection from the tip surface or upon the dissociation of large clusters. The study of multiple detection events supports this interpretation.

Optical Contactless Measurement of Electric Field-Induced Tensile Stress in Diamond Nanoscale Needles.

The application of a high electrostatic field at the apex of monocrystalline diamond nanoscale needles induces an energy splitting of the photoluminescence lines of color centers. In particular, the splitting of the zero-phonon line of the neutral nitrogen-vacancy complex (NV0) has been studied within a laser-assisted tomographic atom probe equipped with an in situ microphotoluminescence bench. The measured quadratic dependence of the energy splitting on the applied voltage corresponds to the stress generated on the metal-like apex surface by the electrostatic field. Tensile stress up to 7 GPa has thus been measured in the proximity of the needle apex. Furthermore, the stress scales along the needle shank inversely proportionally to its axial cross section. We demonstrate thus a method for contactless piezo-spectroscopy of nanoscale systems by electrostatic field regulation for the study of their mechanical properties. These results also provide an experimental confirmation to the models of dielectrics surface metallization under high electrostatic field.

WITHDRAWN: Characterizing Nanoscale Precipitation in a Titanium Alloy by Laser-Assisted Atom Probe Tomography

Atom-probe tomography was performed on the metastable β-Ti alloy, Ti-5Al-5Mo-5V-3Cr wt.% (Ti-5553), aged at 300 °C for 0 to 8 h, to precipitate the embrittling isothermal ω phase. A dependency of precipitate quantification laser pulse energy is found by comparing measurements. Ultraviolet laser pulse energies above ∼30 pJ result in significant complex molecular ion formation during field-evaporation, causing mass spectral peak overlaps that inherently complicate data analyses. Observations and accurate quantification of the ω-phase under such conditions are difficult. The effect is minimized or eliminated by using smaller laser pulse energies. With a small laser pulse energy, Ti-rich and solute depleted precipitates of the isothermal ω phase with an oxygen enriched interface are observed as early as after 1 h aging time utilizing the LEAP 5000X S (77% detection efficiency). We note that these precipitates were not detected below a 2 h ageing time with the LEAP 4000X Si (58% detection efficiency). The results correct the archival literature and the discrepancies are rationalized. The Al concentration in the matrix/precipitate interfacial region increases during aging. Nucleation of the α-phase at longer aging times may be facilitated by the O and Al enrichment at the matrix/precipitate interface (both strong α-stabilisers). The kinetics and compositional trajectory of the ω-phase with aging time are quantified, facilitating direct correlation of the APT data to previously published mechanical testing.

Quantitativeness in laser-assisted atom probe analysis of boron and carbon codoped in silicon

Boron and carbon codoped in polysilicon thin films and carbon implanted in silicon substrates have been examined by laser-assisted atom probe tomography (La-APT). Clusters of dopants were observed in annealed samples. Compared with the results obtained by secondary ion mass spectrometry (SIMS), significant miscounts of both boron and carbon were found in La-APT results. On the basis of measurements using two different La-APT systems, it was suggested that the insufficiency of the multihit capability of the detection systems is an important origin of the miscounts.

Carbides and possible hydrogen irreversible trapping sites in ultrahigh strength round steel

The carbides in ultrahigh strength round steel have been investigated by using laser-assisted atom probe tomography (APT) and high resolution transmission electron microscopy (HRTEM) in this paper. Two kinds of carbides are found and one is iron carbide M6C, where carbide formation elements Cr, Mn and Mo replace partial Fe, while the other is niobium carbide MC, where M includes V and Mo besides Nb. These two carbides, due to their different evaporation field, have various densities in reconstructed image of APT. After correction, the hydrogen content within these two carbides illustrates that M6C cannot trap hydrogen, while MC can. The different behaviors in trapping hydrogen between these two carbides may result from elements Fe or Cr in M6C carbide having weaker affinity for hydrogen than Nb and V have in MC.

Three-dimensional atomic-scale investigation of ZnO-MgxZn1−xO m-plane heterostructures

The structural, compositional, and optical properties of ZnO/MgxZn1−xO m-plane heterostructures are investigated using scanning transmission electron microscopy, laser-assisted atom probe tomography, and micro-photoluminescence. Coupled with electron tomography, atom probe tomography is currently the only technique providing a 3D reconstruction of the position of the atoms of a nanoscale specimen with their chemical nature. The multi-quantum well system investigated exhibits a V-groove grating profile along the a-axis accompanied by the formation of Zn- and Mg-enriched regions corresponding to the edges pointing towards the substrate and towards the upper surface, respectively. The optical signature of these heterostructures has been investigated by performing micro-photoluminescence on atom probe tip specimens. Effective mass calculations based on the 3D microscopy data indicate that the quantum well geometry and barrier composition yield a localization of hole states at the bottom of the V-groove.

Nanometer scale composition study of MBE grown BGaN performed by atom probe tomography

Laser assisted atom probe tomography is used to characterize the alloy distribution in BGaN. The effect of the evaporation conditions applied on the atom probe specimens on the mass spectrum and the quantification of the III site atoms is first evaluated. The evolution of the Ga++/Ga+ charge state ratio is used to monitor the strength of the applied field. Experiments revealed that applying high electric fields on the specimen results in the loss of gallium atoms, leading to the over-estimation of boron concentration. Moreover, spatial analysis of the surface field revealed a significant loss of atoms at the center of the specimen where high fields are applied. A good agreement between X-ray diffraction and atom probe tomography concentration measurements is obtained when low fields are applied on the tip. A random distribution of boron in the BGaN layer grown by molecular beam epitaxy is obtained by performing accurate and site specific statistical distribution analysis.

Short-range atomic ordering in nonequilibrium silicon-germanium-tin semiconductors

The precise knowledge of the atomic order in monocrystalline alloys is fundamental to understand and predict their physical properties. With this perspective, we utilized laser-assisted atom probe tomography to investigate the three-dimensional distribution of atoms in non-equilibrium epitaxial Sn-rich group IV SiGeSn ternary semiconductors. Different atom probe statistical analysis tools including frequency distribution analysis, partial radial distribution functions, and nearest neighbor analysis were employed in order to evaluate and compare the behavior of the three elements to their spatial distributions in an ideal solid solution. This atomistic-level analysis provided clear evidence of an unexpected repulsive interaction between Sn and Si leading to the deviation of Si atoms from the theoretical random distribution. This departure from an ideal solid solution is supported by first principal calculations and attributed to the tendency of the system to reduce its mixing enthalpy throughout the layer-by-layer growth process.

Understanding of Capping Effects on the Tip Shape Evolution and on the Atom Probe Data of Bulk LaAlO3 Using Transmission Electron Microscopy.

Two challenges exist in laser-assisted atom probe tomography (APT). First, a drastic decline in mass-resolving power is caused, not only by laser-induced thermal effects on the APT tips of bulk oxide materials, but also the associated asymmetric evaporation behavior; second, the field evaporation mechanisms of bulk oxide tips under laser illumination are still unclear due to the complex relations between laser pulse and oxide materials. In this study, both phenomena were investigated by depositing Ni- and Co-capping layers onto the bulk LaAlO3 tips, and using stepwise APT analysis with transmission electron microscopy (TEM) observation of the tip shapes. By employing the metallic capping, the heating at the surface of the oxide tips during APT analysis became more symmetrical, thereby enabling a high mass-resolving power in the mass spectrum. In addition, the stepwise microscopy technique visualized tip shape evolution during APT analysis, thereby accounting for evaporation sequences at the tip surface. The combination of "capping" and "stepwise APT with TEM," is applicable to any nonconductors; it provides a direct observation of tip shape evolution, allows determination of the field evaporation strength of oxides, and facilitates understanding of the effects of ultrafast laser illumination on an oxide tip.

Laser-assisted atom probe tomography of Ti/TiN films deposited on Si

Laser-assisted atom probe tomography (L-APT) was used to examine superconducting TiN/Ti/TiN trilayer films with nominal respective thicknesses of 5/5/5 (nm). Such materials are of interest for applications that require large arrays of microwave kinetic inductance detectors. The trilayers were deposited on Si substrates by reactive sputtering. Electron energy loss microscopy performed in a scanning transmission electron microscope (STEM/EELS) was used to corroborate the L-APT results and establish the overall thicknesses of the trilayers. Three separate batches were studied where the first (bottom) TiN layer was deposited at 500°C (for all batches) and the subsequent TiN/Ti bilayer was deposited at ambient temperature, 250°C, and 500°C, respectively. L-APT rendered an approximately planar TiN/Si interface by making use of plausible mass-spectral assignments to N31+, SiN1+, and SiO1+. This was necessary since ambiguities associated with the likely simultaneous occurrence of Si1+ and N21+ prevented their use in rendering the TiN/Si interface upon reconstruction. The non-superconducting Ti2N phase was also revealed by L-APT. Neither L-APT nor STEM/EELS rendered sharp Ti/TiN interfaces and the contrast between these layers diminished with increased film deposition temperature. L-APT also revealed that hydrogen was present in varying degrees in all samples including control samples that were composed of single layers of Ti or TiN.

Influence of laser power on atom probe tomographic analysis of boron distribution in silicon

The relationship between the laser power and the three-dimensional distribution of boron (B) in silicon (Si) measured by laser-assisted atom probe tomography (APT) is investigated. The ultraviolet laser employed in this study has a fixed wavelength of 355nm. The measured distributions are almost uniform and homogeneous when using low laser power, while clear B accumulation at the low-index pole of single-crystalline Si and segregation along the grain boundaries in polycrystalline Si are observed when using high laser power (100pJ). These effects are thought to be caused by the surface migration of atoms, which is promoted by high laser power. Therefore, for ensuring a high-fidelity APT measurement of the B distribution in Si, high laser power is not recommended.

First stages of Ni reaction with the Si(Ge) alloy

The Si(Ge) alloy is currently used in the Complementary Metal Oxide Semiconductor (CMOS) technology, improving device performances, decreasing power consumption, and allowing stress engineering in Si-based devices. If Si(Ge) is used in transistors' source, drain and gate, it is necessary to create ohmic contacts between the first-level metal and Si(Ge). In the current Si-based CMOS technology, ohmic contacts are created via the reaction of a thin Ni(Pt) layer with doped-Si, aiming to form a thin NiSi layer on the Si substrate. A similar process should be used on Si(Ge). In this work, the first stages of Ni reaction with Si(Ge) is investigated using high resolution transmission electron microscopy and laser-assisted atom probe tomography. The first stage of Ni/Si(Ge) reaction leads to the formation of a germano-silicide layer made of Nip(Si1−xGex)q nano-grains exhibiting different structures and compositions. The formation of Nip(Si1−xGex)q phases occurs at temperatures as low as 60 °C. The germano-silicide grains exhibit coherent interfaces with the Si(Ge) layer, and during their growth, a fraction of the Ge atoms initially located in Si(Ge) is pushed from the Nip(Si1−xGex)q/Si(Ge) interface into the Si(Ge) layer, leading to Ge accumulation at this interface. This phenomenon can cause Ge accumulation up to 100%, promoting the incorporation of Ge-pure nanometric inclusions inside the germano-silicide layer.

Laser-assisted atom probe tomography of four paired poly-Si/SiO2 multiple-stacks with each thickness of 10 nm

For the past 10 years, laser-assisted atom probe tomography (APT) analysis has been performed to quantify the near-atomic scale distribution of elements and their local chemical compositions within interfaces that determine the design, processing, and properties of virtually all materials. However, the nature of the occurring laser-induced emission at the surface of needle-shaped sample is highly complex and it has been an ongoing challenge to understand the surface-related interactions between laser-sources and tips containing non-conductive oxides for a robust and reliable analysis of multiple-stacked devices. Here, we find that the APT analysis of four paired poly-Si/SiO2 (conductive/non-conductive) multiple stacks with each thickness of 10nm is governed by experimentally monitoring three experimental conditions, such as laser-beam energies ranged from 30 to 200nJ, analysis temperatures varying with 30–100K, and the inclination of aligned interfaces within a given tip toward analysis direction. Varying with laser-energy and analysis temperature, a drastic compositional ratio of doubly charged Si ions to single charged Si ions within conductive poly-Si layers is modified, as compared with ones detected in the non-conductive layers. Severe distorted APT images of multiple stacks are also inevitable, especially at the conductive layers, and leading to a lowering of the successful analysis yields. This lower throughput has been overcome though changing the inclination of interfaces within a given tip to analysis direction (planar interfaces parallel to the tip axis), but significant deviations in chemical compositions of a conductive layer counted from those of tips containing planar interfaces perpendicular to the tip axis are unavoidable owing to the Si2, SiH2O, and Si2O ions detected, for the first time, within poly-Si layers.

Laser-material interaction during atom probe tomography of oxides with embedded metal nanoparticles

Oxide-supported metal nano-particles are of great interest in catalysis but also in the development of new large-spectrum-absorption materials. The design of such nano materials requires three-dimensional characterization with a high spatial resolution and elemental selectivity. The laser assisted Atom Probe Tomography (La-APT) presents both these capacities if an accurate understanding of laser-material interaction is developed. In this paper, we focus on the fundamental physics of field evaporation as a function of sample geometry, laser power, and DC electric field for Au nanoparticles embedded in MgO. By understanding the laser-material interaction through experiments and a theoretical model of heat diffusion inside the sample after the interaction with laser pulse, we point out the physical origin of the noise and determine the conditions to reduce it by more than one order of magnitude, improving the sensitivity of the La-APT for metal-dielectric composites.

Breaking the icosahedra in boron carbide

Findings of laser-assisted atom probe tomography experiments on boron carbide elucidate an approach for characterizing the atomic structure and interatomic bonding of molecules associated with extraordinary structural stability. The discovery of crystallographic planes in these boron carbide datasets substantiates that crystallinity is maintained to the point of field evaporation, and characterization of individual ionization events gives unexpected evidence of the destruction of individual icosahedra. Statistical analyses of the ions created during the field evaporation process have been used to deduce relative atomic bond strengths and show that the icosahedra in boron carbide are not as stable as anticipated. Combined with quantum mechanics simulations, this result provides insight into the structural instability and amorphization of boron carbide. The temporal, spatial, and compositional information provided by atom probe tomography makes it a unique platform for elucidating the relative stability and interactions of primary building blocks in hierarchically crystalline materials.

Three-dimensional atomic mapping of hydrogenated polymorphous silicon solar cells

Hydrogenated polymorphous silicon (pm-Si:H) is a nanostructured material consisting of silicon nanocrystals embedded in an amorphous silicon matrix. Its use as the intrinsic layer in thin film p-i-n solar cells has led to good cell properties in terms of stability and efficiency. Here, we have been able to assess directly the concentration and distribution of nanocrystals and impurities (dopants) in p-i-n solar cells, by using femtosecond laser-assisted atom probe tomography (APT). An effective sample preparation method for APT characterization is developed. Based on the difference in atomic density between hydrogenated amorphous and crystalline silicon, we are able to distinguish the nanocrystals from the amorphous matrix by using APT. Moreover, thanks to the three-dimensional reconstruction, we demonstrate that Si nanocrystals are homogeneously distributed in the entire intrinsic layer of the solar cell. The influence of the process pressure on the incorporation of nanocrystals and their distribution is also investigated. Thanks to APT we could determine crystalline fractions as low as 4.2% in the pm-Si:H films, which is very difficult to determine by standard techniques, such as X-ray diffraction, Raman spectroscopy, and spectroscopic ellipsometry. Moreover, we also demonstrate a sharp p/i interface in our solar cells.

Laser-induced reversion of δ' precipitates in an Al-Li alloy: Study on temperature rise in pulsed laser atom probe.

The influence of tuning the laser pulse energy during the analyses on the resulting microstructure in a specimen utilizing an ultra-fast laser assisted atom probe was demonstrated by a case study of a binary Al-Li alloy. The decomposition parameters, such as the size, number density, volume fraction, and composition of δ' precipitates, were carefully monitored after each analysis. A simple model was employed to estimate the corresponding specimen temperature for each value of the laser energy. The results indicated that the corresponding temperatures for the laser pulse energy in the range of 10 to 80 pJ are located inside the miscibility gap of the binary Al-Li phase diagram and fall into the metastable equilibrium field. In addition, the corresponding temperature for a laser pulse energy of 100 pJ was in fairly good agreement with reported range of δ' solvus temperature, suggesting a result of reversion upon heating due to laser pulsing. Microsc. Res. Tech. 79:727-737, 2016. © 2016 Wiley Periodicals, Inc.

Quantitative analysis of hydrogen in SiO2/SiN/SiO2 stacks using atom probe tomography

We have demonstrated that it is possible to reproducibly quantify hydrogen concentration in the SiN layer of a SiO2/SiN/SiO2 (ONO) stack structure using ultraviolet laser-assisted atom probe tomography (APT). The concentration of hydrogen atoms detected using APT increased gradually during the analysis, which could be explained by the effect of hydrogen adsorption from residual gas in the vacuum chamber onto the specimen surface. The amount of adsorbed hydrogen in the SiN layer was estimated by analyzing another SiN layer with an extremely low hydrogen concentration (<0.2 at. %). Thus, by subtracting the concentration of adsorbed hydrogen, the actual hydrogen concentration in the SiN layer was quantified as approximately 1.0 at. %. This result was consistent with that obtained by elastic recoil detection analysis (ERDA), which confirmed the accuracy of the APT quantification. The present results indicate that APT enables the imaging of the three-dimensional distribution of hydrogen atoms in actual devices at a sub-nanometer scale.

Atom probe tomography of interfaces in ceramic films and oxide scales

Abstract

Elemental Distribution in Multilayer Systems by Laser-Assisted Atom Probe Tomography with Various Analysis Directions.

Elemental distributions in a magnetic multilayer system with the structure Si substrate/Ta/NiFe/Ru/CoFeB/Ru/NiFe were studied using atom probe tomography (APT) along different analysis directions. The distributions of Ru and B atoms, which require a high evaporation field, were strongly influenced by the APT analysis direction. In particular, B in the CoFeB layer appeared near the interface with the lower Ru layer when the analysis was anti-parallel to the film growth direction, while B atoms were observed at the other side of the CoFeB layer when the analysis was parallel to the film growth direction. Moreover, when the analysis was perpendicular to the film growth direction, a homogenous distribution of B atoms was found within the CoFeB layer. Owing to this B behavior, the underlying Ru layer was affected in both of these analysis directions. In APT measurements of such a multilayer system composed of a stack of different evaporation field materials, evaluation of the elemental distribution around interfaces should be performed from more than one analysis direction.