ARTICLE IN PRESS

Materials Science in Semiconductor Processing 9 (2006) 92–95

FTIR spectroscopic system with improved sensitivity

V.D. Akhmetova,b,, H. Richtera,b
a
IHP, Im Technologiepark 25, 15236 Frankfurt (Oder), Germany
b
IHP/BTU Joint Lab, Konrad-Wachsmann-Allee 1, 03013 Cottbus, PF 101344 Germany
Available online 17 February 2006

Abstract

The problem of the determination of the intensity of weak infrared (IR) absorption bands by differential IR
spectroscopy is considered for the case of a noise-limited sensitivity. A spectroscopic system based on a Fourier transform
IR (FTIR) spectrometer which improves the sensitivity of the IR method by at least 30 times, is described. In the
conventional differential FTIR measurements, only a single pair of spectra (from the analyzed sample and from
the reference) is taken during the whole acquisition time. In contrast, in our system, we take the data interchangeably
from the analyzed pair of sample and reference during the same acquisition time. This ‘‘modulation’’ of samples suppresses
the contribution of the low-frequency noise as well as long-term instabilities in the differential spectrum. The described
system consists of an FTIR spectrometer, a computer-controlled optimized sample changer, and software for fully
automated multiple measurements. The main steps of data processing as well as an example of application of multiple
measurements for a diagnostics of thin wafers are presented.
r 2006 Elsevier Ltd. All rights reserved.

PACS: 07.57.Ty; 78.20.-e; 78.30.-j

Keywords: FTIR; Spectroscopy; Sensitivity; Silicon

1. Introduction trometers. An analyzed pair of sample and corre-

Differential infrared (IR) absorption spectro-
scopy is widely used in semiconductor material
research for the impurity and defect analyses of
both bulk materials and thin layers. Usually,
Fourier transform IR (FTIR) spectrometers serve
for such investigations because of their better
sensitivity in comparison with the dispersive spec-
Corresponding author. IHP/BTU Joint Lab, Konrad-Wachs-
mann-Allee 1, 03013 Cottbus, PF 101344, Germany.
Fax: +49 355 69 4961.
E-mail address: akhmetov@ihp-microelectronics.com
(V.D. Akhmetov).
sponding reference probe is measured sequentially
in a relatively short time, typically from several
minutes to several hours, which depends on the
desired accuracy. Nevertheless, the sensitivity of
commercially available FTIR spectrometers does
not satisfy important requirements of the present
semiconductor material science. The global ten-
dency of device miniaturization as well as the
progress in the performance of bulk materials
causes the reduction of the analyzed sheet density
of impurities or defects and, consequently, the
reduction of the intensity of the detected absorbance
bands. The absorption-induced changes in the
transmittance become comparable to the noise level

1369-8001/$ - see front matter r 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.mssp.2006.01.032
 ARTICLE IN PRESS
V.D. Akhmetov, H. Richter / Materials Science in Semiconductor Processing 9 (2006) 92–95
of the recorded spectra. This noise level strongly
limits the sensitivity of the IR method. Special
probes, up to 10 mm thick, are used for enhancing a
signal-to-noise ratio [1,2]. Such approach is not
suitable for monitoring wafers during semiconduc-
tor processing. Moreover, the intrinsic lattice
absorption strongly limits the thickness of the
samples. A simple elongation of the data acquisition
time does not provide a significant ‘‘refining’’ of the
differential spectra from the noise. This is due to the
increase of the contributions of both low-frequency
noise and long-term instabilities in the recorded
differential spectrum with increasing duration of
measurements.
In this report, we describe a spectroscopic system
based on a FTIR spectrometer, which improves the
sensitivity of the IR method by 30 times or more. In
contrast to the traditional procedure, which in-
cludes a record of only one pair of spectra during
acquisition time, in our system, we take the data
interchangeably from the analyzed pair of samples
during the same acquisition time. The ‘‘modula-
tion’’ of samples suppresses the contribution of low-
frequency noise as well as instabilities of FTIR
spectrometers in the final differential spectrum
calculated from the recorded set of the spectra [3,4].
2. Apparatus and procedure
An evacuated FTIR spectrometer BOMEM DA8
served as a base for our system. Computer
controlled sample changers were designed for
periodical change of samples during data acquisi-
tion. Construction of the sample changers as well as
the speed of moving stages were optimized in order
to reduce an influence of movement of sample
changer on the alignment of Michelson interferom-
eter in the spectrometer.
Special software was created using Array Basic
and C++ allowing to carry out the multiple
measurements together with initial data processing
in a fully automated regime. 16 to 1 million partial
spectra can be measured and numerically treated by
our current software during one multiple measure-
ment procedure. Each exchange of sample in the
sample changer is accompanied by recording a new
spectrum Si, where i is the number of the spectrum.
The system starts with recording the spectrum S0 of
the reference, implying that all further even spectra
belong to the reference and all odd spectra belong to
the analyzed sample. As a result, n pairs of spectra
93
are collected after finishing the procedure of data
acquisition. The parameter n is chosen to be 8-fold.
The obtained sequence of 2n partial spectra Si
(i ¼ 0, 1, 2, 3,y, 2n
2, 2n
1) is treated in the
following manner:
a) Routine analysis: The differential transmission
spectrum T is calculated as a ratio of the mean of
odd partial spectra to the mean of even partial
spectra:
mean of odd spectra
T¼ : (1)
mean of even spectra
b) Determination of achieved photometric accuracy:
The sequence of Si is considered as chronologi-
cally ordered k groups, each containing 2n/k
spectra. The individual differential transmission
spectrum Tj (j ¼ 1, 2,y, k) is calculated for each
of the groups. It is suitable to divide the whole
sequence Si into 4 or 8 groups. The obtained k
curves Tj as well as the mean of Tj (signed as
TT), can be analyzed visually. More quantita-
tively, the Tj are analyzed by means of mean
square deviation
hX
2 . i1=2
sigma ¼ T j
TT ð k ð k
1Þ Þ .
(2)
c) Estimation of residual contribution of the drift: A
pair of artificial differential spectra is calculated
Deven ¼ 0.5(mean of S4i+2)/(mean of S4i) (i ¼ 0,
1, y, n/2 – 1),
Dodd ¼ 0.5(mean of S4i+3)/(mean of S4i+1)
(i ¼ 0, 1, y, n/2 – 1).
Usually, these two curves should coincide one
with another within the accuracy determined by
(2). If such coincidence occurs, the obtained
spectrum T can be divided by the mean of Deven,
Dodd in order to compensate the residual drift if
the drift is remarkable. If a strong difference
between Deven and Dodd is found, it indicates a
possible instability during the measurements,
which could be surface or bulk changes due to
adsorption–desorption, thermal and mechanical
relaxations, photo-induced phenomena, etc.
d) Rejection of bad partial spectra: If an abnormally
low photometric quality of T is obtained after
data processing, the family of n partial differ-
ential spectra ti ¼ S2i+1/S2i (i ¼ 0, 1,y, n
1) is
calculated and analyzed. The pairs of S2i+1 and
 ARTICLE IN PRESS
94 V.D. Akhmetov, H. Richter / Materials Science in Semiconductor Processing 9 (2006) 92–95
S2i spectra corresponding to the revealed abnor-
mally deviated spectra ti are rejected from the
whole set of collected experimental spectra. The
remaining reduced set of Si is analyzed again
starting from Section a).
3. Achieved photometric accuracy and applications
The photometric accuracy of differential spectra
of the described spectroscopic equipment can be
characterized by ‘‘line 100%’’ [5]. This line is defined
as equal to the ratio between two sequentially
recorded spectra of energy of beam of spectrometer
without sample. For an ideal device, this ratio is
exactly equal to 1 (100%). Most straightforward
comparison of such lines 100% obtained by
traditional measurement and by multiple measure-
ments is presented in Fig. 1. For this comparison,
the same set of experimental data consisting of 4096
partial spectra was used for calculating each of the
lines. Line 100% of the traditional measurement
was defined as the ratio of the second half of the
whole set Si (i ¼ 2048, 2049,y, 4095) to the first
one (i ¼ 0, 1, 2,y, 2047). Such data processing
corresponds to the traditional procedure of mea-
surement. Line 100%, which was defined according
to (1) for the modified procedure, demonstrates
clearly the drastic improvement of photometric
accuracy, in the whole presented IR region. This
improvement is more pronounced for regions where
the atmospheric absorption is relatively high, near
Fig. 1. Lines 100% in a wide spectral region derived from
traditional procedure and from multiple procedure of measure-
ments. The acquisition time is the same for both cases.
Fig. 2. Lines 100% after subtraction of the linear background, in
the atmospheric transparency window 700 –1200 cm
1. The right
axis shows the traditional procedure, and the left axis shows the
multiple measurements. (a) Measured without additional IR
filter, the same experimental data as in Fig. 1. (b) Measured with
additional low-pass filter.
1600 and 3600 cm
1, in spite of maintaining the
vacuum of several Torr in the spectrometer during
data acquisition. The more detailed comparison of
the noise in different lines 100% is performed in Fig.
2a. Here, the linear baselines are omitted for clarity.
The vertical scale for the line 100% obtained from
multiple measurements is expanded by a factor of 30
relative to the scale of the line 100% in the
traditional measurement. It is seen from Fig. 2a
that both of curves have the comparable deviations,
indicating a 30-time improvement of signal-to-noise
ratio as a result of multiple procedure. A further
improvement of the photometric accuracy in the
selected spectral region can be achieved by using an
additional IR filter, which cuts off the shorter
wavelengths (Fig. 2b).
The main steps of our statistical treatment,
according to Section b), are illustrated in Fig. 3a,
where the 8 partial lines 100% as well as their
average and confidence interval are drawn. A
confidence interval better than 0.008% can be
reached in all points of the region 700 –1200 cm
1
using the multiple exchange procedure.
The achieved improvement of the photometric
accuracy allows to detect the small absorption
bands in semiconductor materials. An example of
the application of the multiexchange procedure is
shown in Fig. 4 for the case of N detection in Si. In
 ARTICLE IN PRESS
V.D. Akhmetov, H. Richter / Materials Science in Semiconductor Processing 9 (2006) 92–95
Fig. 3. Determination of confidence interval of multiple mea-
surements. (a) Set of 8 lines 100% and (b) mean line 100% and
interval 73 sigma determined from Eqs. (1) and (2).
Fig. 4. Nitrogen-related IR bands determined in a 730 mm thick
Si wafer by multiple measurements with a total acquisition time
of 2 h. The linear slope of the curves is subtracted.
95
this case, the enhanced sensitivity of our equipment
allows to perform N determination in Si wafers with
standard thickness, which do not exceed 1 mm [3]
instead of the specially prepared 10 mm thick
samples.
4. Conclusions
The use of multiple exchanges of samples during
differential FTIR spectroscopic measurements im-
proves the photometric accuracy of differential
spectra under the same acquisition time by more
than 30 times. The developed algorithm of data
processing provides results for the differential
spectrum, the spectral distribution of the confidence
interval, the refining of the set of partial spectra and
the estimation of residual contribution of the drift in
resulted spectrum. It was demonstrated that the
developed system would be of high efficiency for the
study of modern semiconductor materials.
Acknowledgments
We thank M. Ratzke (BTU) for the assistance
with the software, U. Wulf (BTU), N. Inoue (OPU,
Japan) for helpful comments to the manuscript. We
gratefully acknowledge financial support by the
HWP grant of the Federal Government of Germany
and the State of Brandenburg.
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