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Combining electron energy loss spectroscopy and convergent beam electron diffraction
measurements, we have determined the mean-free-path for inelastic electron scattering for
four different aluminium alloys. Electron energy loss spectroscopy spectra were acquired
with the transmission electron microscope in image mode, without any objective aperture
inserted. The value for pure aluminium was determined as 119 ⫾ 5nm at an incident elec-
tron energy of 150keV. For the most common alloys with moderate amounts of alloying ele-
ments, no significant changes in the mean-free-path values are measured within the 5% ac-
curacy of the method. The-mean-free path values are required for accurate determination of
the thickness of thin foils for transmission electron microscopy using electron energy loss
spectroscopy. On the basis of our experimental results, we estimate a single measurement
of foil thickness to have an accuracy of better than 8% if the mean-free-path is known
within 5%. The outlined procedure for thickness measurements is very robust, with thick-
ness results being insensitive to experimental details such as inclination of the specimen or
diffracting conditions. © Elsevier Science Inc., 2000. All rights reseved.
eral minutes per measurement at best), in- deformed over a wide range in the Zener-
volving controlled tilting of the sample and Hollomon parameter (a dimensionless para-
fairly elaborate data evaluation. meter for deformation kinetics that includes
The electron energy loss spectroscopy strain rate, temperature, and activation en-
(EELS) method for measuring sample ergy for dislocation movement). Here, more
thickness is based on a simple relationship than 600 individual samples of were ob-
between the intensity distribution in the tained, each sample involving one thick-
EELS spectrum and the ratio between the ness measurement. Lodgaard and Ryum
sample thickness and a mean free path for (Norwegian University of Science and
inelastic scattering [7]. With use of a paral- Technology, Private Communication, 1998)
lel EELS spectrometer, the method is very carried out a comprehensive study of how
fast, with a recording time of fractions of a the densities of ␣-Al(Fe,Mn)Si dispersoids
second per spectrum, and a data evaluation in a 6082 alloy varied with annealing time
time per spectrum of on the order of 20 s. in the temperature range of 520–550–580⬚C,
The method is, therefore, many times faster which involved approximately 400 thick-
than the alternatives. The real benefit from ness measurements.
this is gained when many thickness mea- The EELS method has potential for being
surements need to be made. For instance, very accurate, although not reaching the
500 thickness measurements using EELS accuracy of 2% or better obtained using
would take about 3 h, whereas the same CBED. The accuracy of the EELS method
number of measurements using CBED or depends on the accuracy with which the
the contamination spot method would take mean free path value is known for the mate-
50 h or more. EELS, therefore, opens up the rial in question, and on the accuracy with
possibility of sampling real distributions of which the intensity of the zero loss peak can
sizes or densities, where the alternative be extracted from the experimental spec-
would have been to obtain only mean trum. Malis et al. [10] established a parame-
values based on a limited number of mea- terized expression for the mean-free-path
surements. Quite large matrices of materi- value based on experimental measure-
als conditions can be studied, without ments on 11 different materials. Using this
thickness measurements being a severe approach, thickness measurements are
time-limiting factor. expected to be accurate within ⫾20% for
Some examples from recent use of the most inorganic specimens, without any ex-
method in projects at our laboratories may plicit calibration of the mean-free-path
illustrate the benefits of having a really fast value being necessary. Considerably better
measurement technique at hand. In [8], we accuracy is within reach, however, if it is
studied deformation structures in a plane- possible, and one takes the trouble, to ex-
strain compressed aluminium alloy (3004) plicitly calibrate the mean-free-path value
to relate these to recrystallization behavior. for the material in question. There are few
The distributions of dislocation density (), reports in the literature on the attainable
subgrain boundary misorientation (), and accuracy in the latter case. Working on an
subgrain size (␦) were measured within the AA3004 aluminium alloy, Botton et al. [11]
different texture components of the mate- found a mean-free-path value of ⫽ 175 ⫾
rial. The work involved obtaining approxi- 5nm at an accelerating voltage of 300kV
mately 200 individual samples of disloca- and a spectrometer collection angle of
tion densities from different regions and 9.5mrad. That is, was determined with an
texture components of the transmission accuracy of 3% by means of combined
electron microscopy specimens, each sam- CBED and EELS measurements.
ple involving one thickness measurement. The motivation for the work reported in
In [9], the distributions of the same , ␦, and this paper was to determine mean-free-
microstructural parameters were mea- path values and accuracies for a selection
sured for a series of materials that had been of aluminium alloys, and to establish a
Measuring Thickness of Aluminum Alloy Thin Foils with EELS 331
where I0 is the intensity of the zero-loss The dependence of p and p on the energy
peak, and Itot is the total intensity in the of the incident electrons and on the plasmon
spectrum. energy Ep is given by Eqs. (8) and (5) [7], and
The most important inelastic scattering the dependence of Ep on the volume density
process is the excitation of volume plas- of conduction electrons (n) by Eq. (9).
mons, i.e., collective oscillations of conduc- 2
σ p ( β ) ≈ Ep ⋅ ln ( β ⁄ θ E ) ⁄ n a a 0 m 0 v (8)
tion electrons [13]. With n ⫽ 1 and i ⫽ plas-
mon scattering in Eq. (2): 2 2 1⁄2
E p = [ ne h ⁄ ε 0 m ] (9)
t ⁄ λ plasmon = I 1 ⁄ I 0 (7)
Here,  is the collection angle, E is the
where I1 is the intensity contained in the characteristic scattering angle, a0 is the Bohr
first plasmon peak. and plasmon have been radius, m0 and m are the rest mass and rela-
shown experimentally to differ by approxi- tivistic mass of the electron, respectively,
mately 30% (see, e.g., [14]), illustrating that and n is the volume density of conduction
other processes than plasmon scattering electrons. Alloying elements in solution
also contribute significantly. The other in- give rise to a changed volume-density of
elastic scattering processes that need to be conduction electrons, Eq. (9), causing shifted
considered are coherent double plasmon Ep, p and p values. The Ep value shows a
excitation, excitation of single conduction linear dependence on solute concentration
electrons, excitation of single core elec- in certain cases, as reported for a number of
trons, and excitation of surface plasmons. alloy systems such as Al–Mg, Al–Mg–Zn,
In addition, the incident electrons undergo Al–Zn, Al–Ag, and Al–Li [15]. As an exam-
phonon scattering. The latter process is ple, we would expect 5% magnesium in
quasielastic (losses less than 100meV) and solid solution to yield a decrease in Ep of
the thermal-diffuse scattered electrons con- approximately 0.25eV, corresponding to a
tribute to the zero-loss peak under the ex- decrease in p of about 2%, Eq. (8).
perimental conditions given by a transmis- Apart from excitation of ordinary volume
sion electron microscope. plasmons, there is also the possibility for co-
It is appropriate here to briefly discuss herent double plasmon excitation, i.e., the
the different scattering processes, the theo- excitation of two plasmons by one electron
retically expected effect of microstructural in a single scattering event [12]. The most
features of the aluminium alloy on the recent literature on this subject [16, 17] agrees
cross sections, and the effects of experimen- that the probability of this process is very
tal parameters such as sample inclination small, with P2/P1 being less than 1–3% (P2
and diffracting conditions. Because the and P1 are the probabilities for coherent
plasmon excitations are collective excita- double plasmon excitation and ordinary
tions of a medium, the cross-sections of plasmon excitation, respectively). In [16], a
these processes depend on the microstruc- review is also given of the wide scatter in
tural state of the alloy. In principle, it reported experimental values for this ratio
makes a difference whether the medium as well as a discussion of possible sources
consists of a single phase with solute at- of error in the different experiments. In the
oms, or if it is a composite medium with present context, this process can be com-
several phases in the form of fine precipi- pletely ignored.
tates, dispersoids, or primary particles in a In addition to the volume plasmons that
matrix. It is convenient to discuss and com- propagate inside the solid, longitudinal
pare the contributions from different scatter- waves of charge density that travel along
ing processes in terms of their cross sections, the surface, i.e., surface plasmons, are ex-
because these are additive [see Eq. (4)]. cited by the incident electron. In the practi-
Volume plasmons in aluminium can be cal case when the metal is covered by a thin
well described by the free-electron theory. layer of surface oxide, the characteristic en-
Measuring Thickness of Aluminum Alloy Thin Foils with EELS 333
ergy of the surface plasmon is Es ⫽ Ep/(1 ⫹ number roughly as ∝ Z1/3, which can be
ε1)1/2, where ε1 is the real part of the dielec- used to estimate how the e–e cross-section
tric permitivity of the oxide. Calculations varies with alloy content.
and experiment confirm that a typical na- For excitation of core electrons (ioniza-
tive oxide thickness of 4nm is sufficient to tion), the scattering cross-sections can be
yield a surface plasmon energy of alumin- treated within an atomic framework to a
ium of Es ⬇ 7eV [18, 19]. For an Al speci- good approximation (although the fine
men with native oxide at normal incidence, structure of ionization edges, of course, can
the probability for surface plasmon excita- depend strongly on bonding and the chemi-
tion is estimated as 2% [7]. The surface cal state of the compound). Hence, ioniza-
plasmon peak is easily visible in spectra tion cross-sections for the alloy can be
from thin specimens, and will be stronger if found by simple averaging of cross-sections
the specimen is tilted (i.e., the incident elec- for the different species, according to the
tron arrives at a non-normal incidence an- overall composition of the probed volume,
gle). A general expression for the effect of and are essentially independent of the
incidence angle on the probability for sur- alloy’s microstructural state and temper.
face plasmon excitation is given in [20]. The Scattering cross-sections for the excitation
total surface plasmon intensity for a given of core electrons can be calculated to good
angle of incidence, integrated over all scat- accuracy using, for example, the hydro-
tering angles, can be derived from this ex- genic model [7] or the Hartree-Slater model
pression, but cumbersome integration is re- [24]. Both approaches are implemented in
quired. the commercial EELS software [25]. The
A competing mechanism to excitation of core-loss scattering process of major rele-
the conduction electrons as plasmons, is the vance in this context is the ionization of
excitation of single conduction electrons aluminium L electrons with an ionization
[7]. These single-electron (e–e) excitations edge onset of approximately 73eV. For al-
involve larger momentum transfer than loys, the core-loss contribution to the total
plasmon excitations and scattering of the scattering cross-section will be an average
transmitted electrons to higher angles than based on the fractions (atomic percentage)
the cutoff angle for plasmon excitation. In a of the alloying elements.
theoretical treatment, Ritchie and Howie Because core electrons are localized close
[20] link the plasmon and high-angle sin- to the atomic nuclei, the excitation of these
gle-electron regimes. Their scattering cross- exhibit channeling effects. That is, an ion-
section reduces to that of plasmon scatter- ization edge will become more or less
ing in the limit of small angles and to that prominent depending on the location in the
of Rutherford scattering from a free elec- unit cell of the atoms being ionized, relative
tron in the limit of large angles. Their to those that lie on the Bragg reflecting
mean-free-paths would suggest that about planes [26]. Hence, the t/ ratio measured
10% of all electrons suffer e–e scattering to by EELS will, in principle, be affected by
a high angle in a thin sample. Eaglesham the diffracting conditions in the probed
and Berger [21] give experimental evidence region of the sample, as given by its crystal-
for single-electron excitations being a sig- lographic orientation with respect to the
nificant contribution to the energy loss electron beam. Calculations of the localiza-
spectrum. For aluminium they find the e–e tion of inelastic scattering by Kohl and
contribution to be comparable to that of Rose [27] show that ionization of alumin-
phonon scattering at room temperature. ium L electrons (onset at ⌬E ⫽ 73eV) is de-
Calculations by Egerton and Wong [22] are localized over more than the unit-cell
in good accordance with this. Their calcula- dimensions. Hence, the channeling effects
tions of e–e cross-sections, using the Lenz on measured t/ ratios are believed to be
model [23], show an increase with atomic small and possibly negligible.
334 A. Bardal and K. Lie
Specimen A was aluminium of 99.5% 164nm. For all points, the measured g
commercial purity, with Fe and Si present value lies within 2 of the mean value,
only in significant amounts as large inter- showing that the CBED results are very re-
metallic particles, and with no significant liable. The standard errors of the single g
amount of alloying elements in solid solu- values range from 23% relative to 3% rela-
tion or as fine scale precipitates. Specimen tive, as indicated with vertical error bars.
B was a 7030 type alloy containing 5 wt.% As expected, the measured g values do not
Zn and 1.2 wt.% Mg. The alloy was given a vary with thickness. The standard errors of
solution heat treatment at 480⬚C for 30 min the single thickness values range from 0.8%
followed by quenching, and aging at 150⬚C realtive to 5% relative, as indicated with
for 2 h. In this peak-aged condition, the ma- horizontal error bars. The average standard
jor alloying elements are present as approx- error of the thickness values was 1.8%.
imately 1 vol.% ZnMg2 precipitates. The All the mean-free-path () values, as ob-
reason for including this alloy was its fairly tained by comparing pairs of CBED thick-
high density of fine precipitates. Although ness and EELS t/ results, are plotted vs.
a volume percentage of around 1% may sample thickness in Fig. 2. There is no vari-
sound quite modest, this is about as high a ation of the values with thickness, show-
value as one may find in the most impor- ing that that the procedure used for extract-
tant 2xxx, 3xxx, 5xxx, 6xxx, and 7xxx alloy ing the values is working. In the plot, the
series. Specimen C was a model alloy of mean-free-path values for specimens A–C
99.99% purity aluminium alloyed to con- appear to be similar, whereas the values for
tain 1.6 wt.% of manganese, and given a so- specimen D, with 5% magnesium in solid
lution heat treatment at 640⬚C for 1 h, fol- solution, appear to be slightly higher. Sta-
lowed by quenching, to bring all the tistical treatment of the data, as summa-
manganese into solid solution. Specimen D rized in Table 1, shows that there are no
was a model alloy of 99.99% purity alumin- significant differences in the values for
ium alloyed to contain 5 wt.% magnesium, specimens A, B, and C. The average value
and given a solution heat treatment at for specimen D is 5% higher compared to
525⬚C for 3 h, followed by quenching, to pure Al (specimen A), but this difference still
bring all the magnesium into solid solution. cannot be termed significant at the level,
All specimens for transmission electron given the accuracy of the measurements. The
microscopy were prepared by mechanical accuracy with which the values are deter-
grinding and polishing, and standard elec- mined are 2–5%.
tropolishing procedures using a Struers Apart from the measured values, we
Tenupol electropolishing unit, a methanol– have also included in Table 1 the measured
nitric acid electrolyte at approximately plasmon energies Ep, the total scattering
⫺30⬚C, medium flow rate, and a potential cross-section total calculated from using
of 20V producing a current near 200mA Eq. (5), and the scattering cross-section for
during thinning. plasmon excitation [calculated using Eqs.
(4) and (7), and the measured Ep value].
Cross-section values were included for the
RESULTS AND DISCUSSION purpose of comparing the relative impor-
tance of different scattering processes. For
Figure 1 shows results of the CBED mea- calculation of the plasmon mean-free-path,
surements, with extinction distance plot- the cutoff angle c was set equal to  in Eq.
ted vs. thickness. The arithmetic mean of (7), and a value of c ⫽ 5mrad was used, on
the measured 220 values is 130 ⫾ 6nm, the basis of the discussion in [7]. p values
which is equal to the theoretical two-beam are found to be typically 9.3 ⫻ 10⫺5nm2,
value of 130nm. The arithmetic mean of the which amounts to approximately 66% of
measured 311 values is 170 ⫾ 10nm, which the total cross section total (typically 14.0 ·
is close to the theoretical two-beam value of 10⫺5nm2). The statistical relative errors in
Measuring Thickness of Aluminum Alloy Thin Foils with EELS 337
FIG. 1. Extinction distances as measured using convergent beam electron diffraction (CBED) plotted vs. thin-foil
thickness.
the calculated p values are equal to those mately 1.5% in p is in good agreement
of the corresponding Ep values, i.e., near with theory, Eqs. (8) and (9).
0.2%. The total uncertainty in the calculated The cross-sections for core-loss excitation
p value (related to the theoretical model) is were calculated using the Hartree-Slater
not known, but any error would yield the model implemented in [25], and the average
same systematic shift for the different al- core-loss cross section for each alloy was
loys. Hence, p for specimen D is signifi- found from the alloy composition. The
cantly lower. It is probably the main contri- edges which were considered were Al K,
bution to the lowered value of total for this Mg K, Mn L, and M, Zn L, and M. The ap-
alloy, but more precise statements cannot proach yields a cross-section of 2.4 ⋅ 10⫺5nm2
be made with the given measurement accu- for all alloys, and no significant differences
racy of (and total). The decrease of ap- between the alloys. This process is seen to
proximately 0.20eV in Ep and of approxi- contribute with approximately 17% to total.
338 A. Bardal and K. Lie
Table 1 Experimentally Measured Mean Free Paths () and Plasmon Energies (Ep) and
Derived Scattering Cross-Sections
Specimen A B C D
t/ ⬍ 1.5, but do not correlate particularly One advantage of working with the TEM
with the CBED errors. The standard devia- in image mode during the EELS recordings
tion of all the [j ⫺ ⬍j⬎]/⬍j⬎ values is is that one should presumably not have to
3.4%. It should then be a good approxima- worry about how the crystallographic ori-
tion to state that the accuracy in ␦Lj/Lj is entation of the probed region of the foil
better than 3%. This is then the precision would affect the measured thickness value,
when making relative comparison between as discussed in the introductory part of this
single thickness measurements from the paper. This presumption was checked ex-
same sample. From (10), the accuracy in a perimentally by making EELS recordings at
single thickness measurement by EELS is some well-defined crystallographic orien-
better than 8% if is known within 5%. tations of the thin-foil specimen. A pair of
FIG. 3. Relative error in single j values, as found from CBED and EELS results. The errors have contributions
from CBED thickness determination (horizontal error bars) and from extraction of I0 from the EELS spectra.
340 A. Bardal and K. Lie
EELS spectra were recorded from a fixed was gradually tilted more and more, and
position on the sample, first with the sam- EELS recordings were made at a fixed posi-
ple oriented at the diffracting condition tion, while ensuring that no strong beams
and then oriented at a nondiffracting condi- were operating in the diffraction pattern.
tion 1–2 degrees off. The conditions checked After correcting for the influence of speci-
were the strongly diffracting (111) and men tilt (␥) on the effective foil thickness
(220) two-beam conditions. Results are dis- (t⬘ ⫽ t/cos␥), variations in measured t/
played in Fig. 4, which shows the ratios be- values could be studied. Results are shown
tween the measured t/ value at the dif- in Fig. 5, for a specimen thickness of ap-
fracting condition and the measured t/ proximately 0.7. No significant variations
value at the nondiffracting condition, plot- with surface inclination are found, i.e., any
ted vs. specimen thickness. All measured possibly increased probability for surface
ratios were found to deviate with less than plasmon excitation does not significantly
approximately 6% from unity, and there affect the results.
are no systematic shifts to above or below When working with aluminium alloys for
unity. There are, furthermore, no systemtic which no explicit calibration of the mean-
variations with specimen thickness. free-path value has been made, fairly accu-
Another measurement series was made rate estimates of can still usually be made
to investigate the effect of the surface orien- based on the present investigation. For most
tation on the mean-free-path. The sample 1xxx, 2xxx, 3xxx, 5xxx, 6xxx, and 7xxx series
FIG. 4. Ratio between t/ with the specimen in a strongly diffracting condition and t/ with the specimen in a
nondiffracting condition.
Measuring Thickness of Aluminum Alloy Thin Foils with EELS 341
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