Atomic resolution composition analysis by scanning transmission electron microscopy

high-angle annular dark-field imaging

E. Carlino, S. Modesti, D. Furlanetto, M. Piccin, S. Rubini, and A. Franciosi

Citation: Appl. Phys. Lett. 83, 662 (2003); doi: 10.1063/1.1592314

View online: https://doi.org/10.1063/1.1592314
View Table of Contents: http://aip.scitation.org/toc/apl/83/4
Published by the American Institute of Physics

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APPLIED PHYSICS LETTERS VOLUME 83, NUMBER 4 28 JULY 2003

Atomic resolution composition analysis by scanning transmission electron

microscopy high-angle annular dark-field imaging
E. Carlino,a) S. Modesti,b) D. Furlanetto, M. Piccin,b) S. Rubini and A. Franciosib)
Laboratorio Nazionale TASC-INFM, Area Science Park, S.S. 14, Km. 163.5, 34012 Trieste, Italy
共Received 28 February 2003; accepted 14 May 2003兲
The silicon concentration profile in Si–GaAs 共001兲 superlattices grown by molecular beam epitaxy
was investigated using scanning transmission electron microscopy high-angle annular dark-field
共HAADF兲 imaging. Comparison with atomic resolution results obtained through cross-sectional
scanning tunneling microscopy indicates that, by choosing appropriate experimental conditions,
HAADF imaging can be used to gauge the Si distribution in GaAs on the atomic scale even without
any image simulation. © 2003 American Institute of Physics. 关DOI: 10.1063/1.1592314兴

Over the years, transmission electron microscopy 共TEM兲
has widely demonstrated its potential to study material struc-
tures with the highest spatial resolution available. More re-
cently, the combination of scanning tunneling microscopy
共STM兲 and high-angle annular dark-field imaging 共HAADF兲
has shown promise as an analytical tool that can provide
chemical information with comparable atomic resolution.
One of the strong advantages of HAADF relative to
other TEM imaging techniques, such as phase-contrast high-
resolution TEM 共HRTEM兲, is related to the mainly incoher-
ent nature of the image obtained by HAADF. As a result,
HAADF images provide unambiguous information on the
position of the atomic columns in a solid with subangstrom
resolution1 equipped with spherical aberration coefficient
correctors. Furthermore, contrast in the HAADF image is
approximately proportional to the square of the average
atomic number of the atomic column,2 so that detailed
chemical information can be directly obtained without the
uncertainty related to the phase problem in HRTEM
imaging.3,4
We explored the potential of high-resolution z-contrast
imaging5,6 to obtain Si concentration profiles in Si–GaAs
共001兲 superlattices. Such test structures were selected be-
cause the expected Si distribution in Si ␦-doped layers in
GaAs and Si–GaAs superlattices is sharp enough to test the
spatial resolution of our method and can be characterized for
comparison also by cross-sectional scanning tunneling mi-
croscopy 共XSTM兲. Moreover, the transition between fully
ionized ␦-doped layers, exhibiting dominant IR and Raman
signatures characteristic of substitutional impurities on Ga
sites (SiGa), and ordered Si–GaAs superlattices,7–9 which
exhibit vibrational and electronic properties consistent with
those expected for ideal, pseudomorphic Si quantum wells in
GaAs, remains poorly understood, so that new experimental
tools might have an important role to play in this area.
We used solid-source molecular beam epitaxy to grow
the samples on GaAs 共001兲 wafers. A total of ten Si layers
were fabricated at 600 °C interrupting the growth of the
GaAs host crystal by closing the Ga shutter, opening the Si
shutter, and leaving the As shutter open. Nominal Si layer
a兲
Electronic mail: elvio.carlino@elettra.trieste.it
b兲
Also at: Dipartimento di Fisica, Universta’ di Trieste, 34127 Trieste, Italy.
thickness in each superlattice period was 1 monolayer 共ML兲,
i.e., 6.26⫻1014 cm⫺2 , deposited at a rate of 0.002 ML/s.
The spacing between the Si layers was 50 nm. A 500-nm-
thick n-GaAs layer was grown to cap the structure. The
GaAs between the layers and up to 10 nm above and below
the superlattice was undoped. The buffer layer below the
stack and the cap layer above were n doped (1.6
⫻1017 Si donors cm⫺3 ).
HAADF STEM experiments were performed on TEM
specimens prepared in 共110兲 cross-section geometry. The
samples were sectioned and mechanically thinned, prior to
achieving electron transparency by Ar ion-beam milling.
The TEM experiments were performed at room tempera-
ture using a Jeol 2010F UHR TEM/STEM electron micro-
scope, with field-emission gun, operating at 200 kV 共␭
⫽0.0025 nm兲, with a measured spherical aberration
coefficient C s of 0.47⫾0.01 mm. Hence, the relevant inter-
pretable resolution limit in HRTEM is 0.19 nm.10 The STEM
attachment is equipped with a bright-field detector and a
YAP HAADF detector for high-resolution z-contrast imag-
ing. The theoretical resolution achievable in z-contrast mode
with the available electron optics is 0.126 nm.11
Figure 1 shows a low magnification HAADF image in
关110兴 zone axis of the epilayer. The collection angle was
84⭐2␪ ⭐224 mrad as in all the HAADF images here re-
ported. Due to the lower atomic number of Si relative to
GaAs, the ten Si layers give rise to the sharp dark lines
spaced by 50 nm in GaAs. The monotonic decrease in inten-
sity in going from the bottom-right to the top-left section of
the image is due to the specimen thickness variation over the
relatively wide area of the low-magnification micrograph.
Figure 2共a兲 shows an atomic resolution HAADF image
of one of the Si quantum well regions. The growth direction
is marked in the image and the TEM specimen thickness in
this area was 15.0⫾1.5 nm, as measured by convergent beam
electron diffraction. The signal-to-noise ratio of the image in
Fig. 2共a兲 is remarkably good even if a comparatively large
collection angle was used. As reported by Treacy et al.,12 a
collection angle higher than 80 mrad allows acquisition of
mainly incoherent electrons in the HAADF image and, in our
case, eliminates contributions to the image contrast due to
strain at the Si–GaAs interface, where the high mismatch

0003-6951/2003/83(4)/662/3/$20.00 662 © 2003 American Institute of Physics

Appl. Phys. Lett., Vol. 83, No. 4, 28 July 2003
FIG. 1. Low magnification HAADF image in 关110兴 zone axis of the whole
epilayer.
between the Si and GaAs lattice parameters is expected to
yield diffraction effects.13
The bright spots in Fig. 2共a兲 give unambiguously the
position of the atomic column projected along the 关110兴 di-
rection. In fact, the intensity in a HAADF image is given by
I(r)⫽O(r) * P 2 (r) where O(r) is the object function and
P 2 (r) is the resolution function.14 The image is hence
formed incoherently with negligible phase contrast effect. In
an atomic resolution z-contrast STEM experiment the avail-
able resolution is therefore due to the size of the object func-
tion, O(r), convoluted with the size of the resolution func-
tion, P 2 (r), where the latter is the size of the electron beam
scanned on the specimen.15 The combined effect of the use
of an annular STEM detector with a collection angle larger
than 80 mrad and thermal diffuse scattering, relevant at high
scattering angle,16 produces an image in which the main con-
tribution is given by the 1s columnar states.17 The 1s colum-
nar Bloch states are ideal if the aim is to solve the position of
the atomic columns as they are the less dispersed around the
positions of the atomic columns with a full width at half
maximum 共FWHM兲 of only 0.06 –0.08 nm.15 Emphasizing
the 1s columnar states provides the best picture and the ul-
timate resolution achievable in an atomically resolved TEM/
STEM experiment.
Since the HAADF contrast is strongly affected by the
average atomic number of the atomic column, the image in
Fig. 2共a兲 contains direct chemical information that can be
used to probe the Si concentration profile within the GaAs
matrix directly from the as-acquired HAADF images. In Fig.
2共b兲 we plot, in arbitrary units, the experimental contrast
observed from data such as those depicted in Fig. 2共a兲, as a
function of the distance from the interface. In order to in-
crease the signal-to-noise ratio, the intensity profile in Fig.
2共b兲 was obtained by integrating the multiscan camera output
Carlino et al. 663
FIG. 2. 共a兲 High-resolution z-contrast HAADF image in 关110兴 zone axis of
a Si quantum well. 共b兲 Intensity profile 共a.u.兲 as measured on the image in
Fig. 2共a兲.
for about 3 nm in the direction parallel to the Si/GaAs inter-
face.
The distance between two consecutive peaks in Fig. 2共b兲
is 0.28 nm, in agreement with the expected cation or anion
spacing in the bulk along the 关001兴 direction. The higher
peaks, 1.5 nm away from the minimum in the intensity pro-
file, reflect the higher atomic number of the III–V species.
The intensity decrease observed in going from the GaAs re-
gion toward the metallurgical Si–GaAs interface is due to
the presence of Si in the atomic columns. Hence, the distri-
bution of Si atoms shows a FWHM of about 1.2 nm. Fur-
thermore, the Si distribution is slightly asymmetric with a
somewhat broader distribution toward the bulk. This result is
representative of several measurements performed on STEM
HAADF images.
To draw quantitative comparisons, the same samples
were examined by XSTM. Wafers mechanically thinned
down to 0.1 mm, were cleaved in an ultrahigh-vacuum
STM—immediately prior to image acquisition—to expose
atomically flat, electronically unpinned 兵110其 surfaces nor-
mal to the 关001兴 growth direction. STM tips were obtained
from a W wire electrochemically etched in NaOH, heated to
1000 °C in UHV and sputtered with Ar ions in situ.
Figure 3共a兲 shows constant–current STM micrographs of
664 Appl. Phys. Lett., Vol. 83, No. 4, 28 July 2003
one of the Si quantum well regions, recorded with a negative
sample bias of 1.7 V. Constant–current STM micrographs of
the 共110兲 cleavage surface intersecting the Si monolayers
acquired for negative samples bias voltages 共1.6 –2.5 V兲
show the Si-rich layers as brighter regions, with a ⬃0.1 nm
higher elevation relative to the neighboring GaAs surface.
The elevations are surrounded by small depressions 共darker
zones along the interface兲. The elevations disappear in the
images recorded positive sample bias, and therefore are not a
topographic effect, but are caused by a local change of the
electronic properties induced by the Si atoms. Tunneling
spectroscopy data indicate that the depressions on either side
of the Si-rich regions are caused the local potential induced
by the Si layer.
The dotted line in Fig. 3共b兲 depicts the density of the
bright surface unit cells observed in several XSTM images at
negative sample bias as a function of the distance from the
interface. The edges of the bright regions are sharp, therefore
these regions are not caused by subsurface impurities which
give rise to diffuse features,18 but by surface Si atoms. If we
assume that each bright surface unit cell is associated with
one Si surface atom, the measured Si content in the quantum
well is then 1.2 ML.
To compare HAADF and XSTM data, we plot in Fig.
3共b兲 共solid line兲 the inverted average shift of the STM tip
normal to the surface ⌬z as a function of the distance from
the interface along the 关001兴 direction. The profile in Fig.
3共b兲 shows the short period oscillation induced by the sur-
face As atoms, spaced by 0.56 nm along the 关001兴 direction.
Superimposed to these oscillations there is the minimum
caused by the Si layer—where ⌬z is proportional to the con-
centration of Si on 共001兲 planes—and two maxima caused by
the local electrostatic potential. The slight asymmetric broad-
ening of the Si distribution toward the bulk observed in Fig.
2 is more clearly observed in the dotted curve in Fig. 3共b兲,
while the inverted average shift of the STM tip 共solid line兲 is
also affected by the gradient of the local electrostatic poten-
tial.
As it can be seen by comparing Figs. 2共b兲 and 3共b兲, there
is excellent agreement between the z-contrast STEM and
XSTM results. This indicates that, by choosing the appropri-
ate experimental conditions, HAADF imaging can be used to
probe the Si distribution in GaAs with atomic resolution
from the raw data, even without any image simulation.
The measured value of the FWHM of the Si density
distribution is 1.2 nm. Individual subsurface charged Si do-
nors, visible in the XSTM images with a density distribution
Carlino et al.
FIG. 3. 共a兲 XSTM images of the intersection of the Si
plane with the 共110兲 cleavage surface. Tunneling cur-
rent was 0.2 nA, sample bias ⫺1.7 V; label D denotes a
cleavage defect. 共b兲 solid circles: distribution of the Si
concentration in the 共001兲 planes as a function of the
position along the 关001兴 growth direction, calculated
from the density of the bright unit cells; solid line: in-
verted ⌬z profile from the images in Fig. 3共a兲.
about four times wider and asymmetrically broadened to-
ward the surface, account for only 1% of the nominal
concentration.19 We speculate that the slight asymmetric
broadening toward the bulk of the Si distribution within the
superlattice layers could reflect a repulsive interaction be-
tween the two Si species, mediated by strain and/or electro-
static forces.
Independent calibrations of the Si content could also be
achieved in the future by comparing HAADF data with
simulated results, or fabricating and studying a region of
pure Si within the epilayer.
This work was supported in part by INFM under the
Progetto di Ricerca Avanzato XSTMS and by NSF under
Grant No. DMR-9819659.
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