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surface science
ELSEVIER Applied Surface Science 87/88 (1995) 305-310

A method for reconstructing and locating atoms on the crystal lattice in three-dimensional atom probe data
Patrick P. Camus a,h,,, David J. Larson

b,c, Thomas

F. Kelly a,b,c

a Department of Materials Science and Engineering, University of Wisconsin, Madison, WI 53706, USA b Applied Superconductivity Center, University of Wisconsin, Madison, WI 53706, USA c Materials Science Program, University of Wisconsin, Madison, WI 53706, USA

Received 10 July 1994; accepted for publication 26 August 1994

Abstract The physical process of field evaporation introduces lateral aberrations in the ion trajectories toward an atom probe detector. In three-dimensional atom probes, these aberrations blur information describing the 3D atomic stacking in the material. This work reports progress that has been made using Fourier transform and pattern recognition techniques to reconstruct an original lattice structure from simulated atom probe data and to subsequently force atoms to the nearest lattice point. Usually Fourier transform techniques are used in image processing to separate image noise from periodic information not to actually shift features in the image. The present technique analyzes a 2D data set and determines the statistically best lattice parameters, lattice orientation, lattice position and site occupation with no free parameters in the analysis. A randomly oriented Gaussian blurring function is used to simulate trajectory aberrations. For 151 atoms originally on a square lattice, atom locating errors are less than 4% when the mean displacement is one quarter of the lattice parameter. The repositioning efficiency increases rapidly with increasing data set size and decreases rapidly with increasing aberration magnitude.

1. Introduction The ultimate three-dimensional atom probe (3DAP) would have sufficient spatial resolution such that the crystal structure o f a material could be determined directly from the detected atomic positions. Aberrations in the trajectories of ions evaporated from the specimen are the primary limitation on the lateral resolution o f A P analyses [1]. These aberrations were first observed in field desorpfion microscopy b y the appearance of bright and dark

* Corresponding author. Fax: + 1 608 263 3704; E-mail: ppca mus@apm2.msae.wisc.edu.

lines in the image of pure materials [2] and later were described for two-phase materials [3]. These features were usually attributed to a focusing effect or " r o l l - u p " of the evaporating atom on its neighbors during evaporation. The contrast depends markedly on local atomic arrangement and electronic behavior. Trajectory aberrations in desorption images of two-phase materials have been described by local magnification effects. The contrast is usually attributed to local evaporation behavior. Because there are no theoretical descriptions beyond the " r o l l - u p " and local magnification effects, and there has been little empirical work, it is not likely that these aberrations m a y be corrected on a purely first-principles theoretical basis in the near future.

0169-4332/95/$09.50 1995 Elsevier Science B.V. All rights reserved

SSDI 0169-4332(94)00503-6

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The magnitude of these aberrations are unknown but are expected to be in the range 0.1-0.5 nm. The radial variation is uncertain, but over small fields of view may be systematic. If the magnitude of the aberrations is relatively small and the radial variation is systematic, then pattern recognition image processing techniques may be used to investigate the removai of the aberrations and to image the true underlying structure. Thus, more information may be obtained from the image than is visually apparent. Pattern recognition techniques are used when systematic information must be extracted from a whole scene or background noise needs to be reduced [4]. First a search pattern is chosen; the position(s) of which will be sought in the data set. The location of this pattern within the data set is usually found by performing a 2D cross-correlation analysis between the pattern and the data. This gives an array of the statistically best position(s) of the search pattern with respect to the data. Computationally, this is accomplished by (1) taking the Fourier transform (FT) of both the pattern and the data, (2) multiplying one FT with the complex conjugate of the other FT and (3) taking the inverse FT. High intensity regions in the resultant array are the positions of pattern matching. Analysis of 3DAP data requires extra computation both prior to the cross correlation and afterward. The first problem occurs because the search pattern to be matched is a lattice, which typically is unknown. The lattice can be determined by calculating a diffraction pattern from the data and measuring the lattice parameters and the relative orientation with respect to the original data set. The second problem arises because the atoms must be moved onto the lattice sites. The cross-correlation gives the relative position of the lattice with respect to the data, but the atoms are still at aberrated positions, not at lattice points. Minimization of all atom displacements to the nearest lattice positions for the whole data set would hopefully return the atoms to their proper lattice sites. At this stage, all detected atoms would be at their original location within the crystal and analysis of the structure (usually site occupation probability) would commence. Fundamental problems encountered with this technique include accounting for interstitial atoms, ionic clusters and the potentially large magnitude of trajectory aberrations. Interstitial atoms must not be

used for determination of the crystal lattice nor for atomic displacements to lattice positions. However, after the lattice has been determined, an interstitial sub-lattice may be determined and the atoms placed on it. Ionic clusters of sample atoms could be placed on whichever lattice seems to make the most sense, depending upon the type of atoms in the cluster, or could be ignored initially. If the aberrations are very large, then it may be impossible to determine a lattice because too much displacement occurred and the information about the underlying lattice cannot be extracted. In this case, the analysis cannot be completed without a priori information about the lattice parameters a n d / o r orientation. Fortunately this often may be available. Theoretical or empirical work on trajectory aberrations is required to determine the general applicability of this technique.

2. Methodology
A 2DAP data set was fabricated of points on a square lattice at a particular simulated positioning resolution. The effect of microchannel plate efficiency on the data was introduced by randomly removing 40% of the atoms to simulate actual detection efficiencies. This produced a sparse 2D array, Fig. la. Trajectory aberrations introducing positioning errors were simulated by applying a two-dimensional spatial Gaussian distribution with full width at half maximum of a specified o- on the atom positions at each lattice site. The appearance of the resultant data set, Fig. lb, is very similar to that obtained from 3DAPs [5,6]. To independently obtain the lattice parameters, a diffraction pattern was calculated for the data set, Fig. lc. The two lattice parameters, the angle between the crystal axes and the relative orientation of the lattice with respect to the data set may all be determined directly from this pattern. A reference lattice constructed from these values is used as the pattern to be matched in the cross-correlation calculation. Since the lattice is periodic, the resultant cross-correlation array is also periodic with a period of one unit cell, Fig. ld. Now the correctly sized, oriented and positioned lattice is used as a reference for locating the detected atoms on lattice sites.

P.P. Camus et al. /Applied Surface Science 8 7 / 8 8 (1995) 305-310

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Fig. 1. Steps in the pattern recognition i m a g e processing of simulated 2DAP data set of 16 16 unit cells of size 8 8 bins with o" = 2. (a) Original data set with 60% detection efficiency. (b) Application of 2D spatial Gaussan distribution to (a). (c) 2D diffraction pattern from which the x and y lattice parameters are measured (spot diameter corresponds to intensity). (d) 2D cross-correlation coefficient between calculated lattice and (b). (e) A t o m s m o v e d to nearest calculated lattice sites. (f) Resolution of double lattice site occupancy (diamonds) overlaid on original atom positions from (a) (open squares).

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P.P. Camus et al. /Applied Surface Science 8 7 / 8 8 (1995) 305-310

To obtain the best lattice locations for all of the atoms simultaneously, the total distance that each atom moves must be minimized. This requires that the distance of each atom to its neighboring lattice positions be measured and the atoms eventually moved to those lattice sites that produce the cumulative minimum displacement, Fig. le. This analysis does not always produce acceptable results in that two atoms may be moved to the same lattice site. Resolution of this problem requires an additional least-squares computation which then minimizes the locating distance of these atoms to neighboring lattice sites while maintaining unique lattice positioning, Fig. if. Sometimes this causes a "chain reaction" in which subsequent calculations are required. At this point, all of the atoms should be uniquely and accurately positioned within the crystal as they were in the original sample. Note that no free parameters are necessary to achieve this result.

when the average aberration becomes greater than half the interatomic distance. A complete analysis is presented in Fig. 1 for a 16 16 data set of 8 8-bin (a 0) unit cells, 60% detection efficiency and spatial distortion through application of a radially symmetric Gaussian using o-= _ 2 bins. The lattice parameters could easily be determined from measuring the spacing of the nearest peaks in the diffraction pattern, Fig. lc, which matched exactly the initial known values. These values were used to construct the calculated lattice and for the cross-correlation analysis. The peak in

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A number of parameters must be chosen in order to simulate the 2DAP data set. The size and shape of the unit cell, the resolution of the atomic placements, the number of unit cells in each direction, the radial shape of the aberrations and the magnitude of the aberrations were assigned values which were either physically realistic or computationally workable. The data set encompassed 16 16 unit cells, each of which consisted of typically 8 8 bins on a square lattice. The magnitude of the aberrations was varied from o-= 0 to 4 bins in both x and y directions. The first simulation investigated the effect of aberration magnitude on atomic positioning ability. When the initial data set was 8 8 unit cells, the lattice could be determined from the diffraction pattern for o-= 1 bin; but at or = 2 bins, the aberrations were too large to extract the lattice parameters from the diffraction pattern. When the size of the data set was increased to 16 16 unit cells, the lattice could be determined using the larger deflection. This indicates that there is not enough information in the smaller data set for successfifl extraction of the lattice. In general, the larger the data set, the larger the aberrations that may be tolerated without losing the periodicity. The upper limit on this may still be

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P.P. Camus et al. /Applied Surface Science 8 7 / 8 8 (1995) 305-310

309

the cross-correlation at (4.5, 4.5), Fig. ld, was very close to the expected (4, 4) offset of the original data. Location of the atoms to nearest lattice sites produced 7 doubly occupied lattice sites, Fig. le, that required further analysis. Resolution of these conflicts produced placement of most of the atoms on their original position but left 6 atoms out of 151 misplaced, Fig. lf. Thus, the correct lattice size, shape, orientation and relative position were obtained with the error in atom positioning of less than 4%. At a distortion of or = 2, lattice parameters could not be determined for a unit cell of 6 8 bins whereas they could be determined for a unit cell of 10 8 bins, Fig. 2. This shows that the ratio of ~r/a o must be low to perform this analysis. More atoms in the data set may increase the signal sufficiently that this ratio may be increased. This suggests that higher resolution of actual ion arrival positions may be helpful in deconvoluting 3DAP data. When the initial data set is rotated 30 , the resultant diffraction pattern is also rotated the same 30 , Fig. 3, as it should be. This confirms the usefulness of this technique to determine the orientation of the sample with respect to the detector. It also means that high resolution angular analyses may be performed on data sets obtained from a polycrystalline analysis by analyzing two separate regions of the data set. Most of the limitations that occur with this analysis originate from trying to independently determine the lattice parameters and orientation with respect to the data set. If this information can be obtained a priori, usually via electron diffraction in electron microscopy, then that information may be used in construction of the lattice. This will reduce the uncertainty in the lattice construction and may enable site determinations when not otherwise possible. Although this analysis was performed using 2D data, the above quasi-optical filtering technique may be readily extended to 3D. Initial calculations indicate that increasing the size of the data set should permit the analysis of data with greater trajectoryaberration magnitudes. The much larger data sets of 3DAP analyses, typically 10 6 atoms or more, is expected to provide a significantly larger signal-tonoise ratio than these preliminary calculations using between 151 and 256 atoms. Although actual images have not yet been analyzed, these analysis proce-

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dures clearly hold promise for real-space structure determination for 3DAP. Furthermore, real aberrations are not random and this technique holds good promise for determining the magnitude and direction of real aberrations, at least on a local scale.
4. C o n c l u s i o n s / f u t u r e work

Fourier transform and pattern recognition t e c h niques have been used to reconstruct an original lattice structure from simulated 3DAP data and to subsequently force atoms to the nearest lattice site This technique analyzes a 2D slice and provides the statistically best lattice parameters, lattice orienta-

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P.P. Camus et al. /Applied Surface Science 8 7 / 8 8 (1995) 305-310

tion, lattice position and site occupation with no free parameters in the analysis. Atom positioning errors for simulated data structures are less than 4% with the parameters used. The quality of the results are highly dependent on the size of the data set and the magnitude of the aberrations. Extension of this technique to 3D data sets only involves computational complexity not a change in the algorithm. Interstitial ionic species and ionic clusters must be treated carefully so that they do not adversely affect the lattice determination. General applicability of this technique to real data sets depends upon the magnitude of the real aberrations which are not adequately described either theoretically or empirically at the present time.

Hurt and Dr. Lance Haworth). The authors would like to thank L.M. Holzman for helpful discussions.

References
[1] M.K. Miller and G.D.W. Smith, Atom Probe Microanalysis: Principles and Applications to Materials Problems (Materials Research Society, Pittsburgh, PA, 1989) p. 79. [2] A.R. Wangh, E.D. Boyes and M.J. Southon, Surf. Sci. 61 (1976) 109. [3] M.K. Miller, J. Phys. (Pads) 48-C6 (1987) 565. [4] J.C. Russ, The Image Processing Handbook (CRC Press, Boca Raton, FL, 1992) p. 218. [5] A. Cerezo, T.J. Godfrey, C.R.M. Grovenor, M.G. Hetherington, R.M. Hoyle, J.P. Jakubovics, J.A. Liddle, G.D.W. Smith and G.M. Won-all, J. Microsc. 154 (1989) 215. [6] B. Deconihout, A. Bostel, P. Bas, S. Chamberland, L. Letellier, F. Danoix and D. Blavette, Appl. Surf. Sci. 76/77 (1993) 145.

Acknowledgements
This work is sponsored by the National Science Foundation under grant No. DMR-8911332 (Dr. John