Surface & Coatings Technology 201 (2007) 9359 – 9364

www.elsevier.com/locate/surfcoat

FTIR characterization of light emitting Si-rich nitride films prepared

by low pressure chemical vapor deposition
V. Em. Vamvakas ⁎, S. Gardelis
Institute of Microelectronics, NCSR “Demokritos”, P. O. Box 60228, 15310 Aghia Paraskevi, Athens, Greece

Available online 4 May 2007

Abstract

We report on the infrared transmission and light emission of Si-rich nitride (SRN) films prepared by low pressure chemical vapor deposition
(LPCVD) from dichlorosilane (SiH2Cl2, DCS) and ammonia (NH3) mixtures. The main absorption band at about 830 cm− 1, attributed to Si–N
vibration mode and observed in stoichiometric silicon nitride, shifted to slightly higher wavenumbers with increasing Si content in the SRN films.
Annealing at temperatures higher than the deposition temperature induced a further shift of the main band to higher wavenumbers. Additionally, a
new band appeared as a “shoulder” at about 1080 cm− 1, attributed to partial oxidation of the silicon nanocrystals. Photoluminescence (PL)
obtained from the SRN films increased considerably and shifted to shorter wavelengths as the Si content decreased whereas annealing caused
further enhancement and a slight shift to shorter wavelengths in comparison with the as-grown films.
© 2007 Elsevier B.V. All rights reserved.

PACS: 78.30.-j; 78.55.-m; 78.67.Bf

Keywords: Silicon nitride; Silicon nanoparticles; FTIR spectroscopy; Photoluminescence

1. Introduction annealing caused the formation of Si–O bonds even though

Stoichiometric silicon nitride films are widely used in silicon
based micro- and nanotechnology as barriers to sodium diffusion
and as masking layers for the local oxidation of Si in ULSI
technology [1,2]. In addition their excellent optical properties
make them suitable for optical waveguides and for antireflective
and protective coatings for solar cells [3–6]. The introduction of
extra silicon in silicon nitride films was firstly used to lower or
reverse the residual stresses of these films [7–9] making possible
the development of suspending membranes in micro-mechanical
systems. Other applications of Si-rich nitride (SRN) films in-
clude the typical Oxide–Nitride–Oxide (ONO) memory device
[10–14] and photonic devices [15–22].
In this work SRN films were grown by low pressure chemical
vapor deposition (LPCVD) using SiH2Cl2 (DCS) and NH3 mix-
tures in order to study their light emission properties in com-
bination with FTIR analysis. All films were deposited at 800 °C
and then annealed at 950 °C and 1100 °C in dry nitrogen for times
ranging between 30 min and 4 h. FTIR analysis showed that
⁎ Corresponding author. Tel.: +30 210 6503117; fax: +30 210 6511723.
E-mail address: v.vamvakas@imel.demokritos.gr (V.Em. Vamvakas).
0257-8972/$ - see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.surfcoat.2007.04.069
precaution was taken to avoid the presence of oxygen during the
annealing process. This indicated that SRN films could be very
easily oxidized. The films emitted light in the visible at room
temperature. The light emission characteristics depended on the Si
content of the films and the post-annealing treatment.
2. Experimental details
All depositions were carried out in a Tempress Systems Inc.
(model omega junior), horizontal hot wall reactor at 800 °C,
230 mTorr. NH3 flow ratio was kept constant whereas DCS flow
ratio varied in order to deposit films with different stoichio-
metries. The deposition parameters are summarized in Table 1.
Before deposition Si substrates were cleaned in a 1:1 H2SO4:
H2O2 solution followed by a dip in hydrofluoric acid (HF)
solution, rinsed in de-ionized water and blown dry with dry
nitrogen. All studied films had thickness of about 100 nm. Post-
annealings were performed at 950 °C and at 1100 °C for 30 min,
1, 2 and 4 h in a furnace in dry nitrogen (N2 99.996%, O2 b
1 ppm, H2O b1 ppm) flowing at a rate of 3.5 slm (standard liters
per minute). Before annealing all samples were cleaned in 1:1
H2SO4:H2O2 solution, rinsed in de-ionized water, blown dry
9360 V.Em. Vamvakas, S. Gardelis / Surface & Coatings Technology 201 (2007) 9359–9364

Table 1
Deposition parameters, refractive index n at 632.8 nm and Si/N ratio of the
deposited films
T (°C) P (mTorr) φDCS (sccm) φNH3 (sccm) n Si/N
Stoichiometric 800 230 20 60 2.02 0.75
Silicon rich 800 230 13.8 5.5 2.15 0.86
800 230 27.5 5.5 2.28 1.10
800 230 55.0 5.5 2.51 1.35

with dry nitrogen and then inserted in the furnace where they
remained for 30 min at 300 °C. This procedure was followed in
order to exclude the possibility of partial oxidation of the
samples due to remaining humidity after the last rinse.
Fourier transform infrared (FTIR) spectra were recorded in
transmission mode using a Bruker (model Tensor 27) single
beam spectrometer. Before recording the spectrum, the
background was taken placing a freshly cleaned piece of silicon
cut from the same silicon wafer used as the substrate. This was
performed in order to eliminate absorption of the substrate
caused by the vibration of the Si–Si bond which gives a peak at
611 cm− 1 and the interstitial oxygen which gives a peak at
1108 cm− 1 [23,24]. Photoluminescence was performed at room Fig. 1. FTIR transmission spectra of the as-grown SRN films with different Si
temperature using for excitation the 458 nm line of an Ar+-ion content.
laser. The signal was analyzed by a Jobin-Yvon spex HR-320
spectrometer and detected by a photomultiplier tube.
Annealing of SRN films with Si/N ratios 1.35 and 1.10 at
3. Results and discussion temperatures higher than the deposition caused a slight shift of
the main absorption band to higher wavenumbers followed by a
The increase of the Si content of silicon nitride films results broadening. In addition, a second band appeared, as a
in an increase of the refractive index of the films compared to “shoulder” to the main band, at 1080 cm− 1. We note here that
the stoichiometric ones [1]. The last two columns of Table 1 spectra obtained from stoichiometric silicon nitride films and
give the refractive index for our films at 632.8 nm and the SRN films with Si/N equal to 0.86 annealed together with the
expected Si/N ratio according to the literature [1].
Fig. 1 shows the FTIR transmission spectra of the as-grown
SRN films investigated in this study. The strong absorption
band located at about 830 cm− 1 corresponds to the asymmetric
stretching mode of vibration of the Si–N bond. There is also a
weak band located at about 480 cm− 1 which corresponds to the
rocking mode of vibration of the Si–N bond. However, the
study of this band is difficult with our equipment since it is
located close to the lower band limit of our spectrometer. In
addition the study of the low energy band does not offer any
extra information thus we focus our study on the main
absorption band. No Si–H or N–H or any other impurity
related vibration mode was detected between 4000 cm− 1 and
400 cm− 1.
The main absorption band of the stoichiometric silicon
nitride film was located at 832 cm− 1. For the SRN films this
band shifted slightly to higher wavenumbers. Specifically, in the
film with Si/N ratio 1.1 this band appeared at 840 cm− 1 whereas
in the film with Si/N ratio 1.35 it appeared at 842 cm− 1. For
films with Si/N ratio 0.86 it appeared at almost the same
position as that of the stoichiometric film, indicating that FTIR
transmission measurements could not distinguish films with
these stoichiometries. The observed shift of the Si–N vibration
mode in the SRN films is expected to be due to the presence of Fig. 2. FTIR transmission spectra of SRN films with Si/N = 1.35 after deposition
the extra Si in the films. and after annealing for 4 h at 950 °C and 1100 °C.
 V.Em. Vamvakas, S. Gardelis / Surface & Coatings Technology 201 (2007) 9359–9364 9361

Table 2
Position of the main absorption band for silicon nitride films of several stoichiometries
Main absorption band (cm− 1)
After deposition Annealed
950 °C 1100 °C
30 min 1h 2h 4h 30 min 1h 2h 4h
Stoichiometric (Si/N) 0.75 832 832 832 832 832 832 832 832 832
SRN (Si/N) 0.86 832 832 832 832 832 832 832 832 832
1.10 839 839 840 841 842 845 845 846 846
1.35 842 845 846 847 847 851 852 853 853
All films have a thickness of about 100 nm.

previously mentioned SRN films remained unchanged before
and after annealing, showing that annealing affected slightly if
not at all their chemical composition. In the following we focus
on the main absorption band of the annealed SRN films with Si/
N ratios 1.35 and 1.10. In the film with Si/N ratio 1.10 the main
absorption band shifted from 839 cm− 1 to 842 cm− 1 after
annealing at 950 °C for 4 h. The same band shifted to 846 cm− 1
after annealing at 1100 °C for 4 h. In the film with Si/N ratio
1.35 the shift of the main absorption band after annealing was
even more distinct. Specifically, annealing at 950 °C for 4 h
resulted in a shift of the band from 842 cm− 1 to 847 cm− 1 while
annealing at 1100 °C for 4 h caused the same band to appear at
853 cm− 1 (Fig. 2). Annealing at temperatures higher than the
growth temperature, which promotes segregation of Si into
nanoparticles and some of them into nanocrystals, as we have
observed previously in similar SRN films [25], is expected to
cause changes in Si–N vibration modes due to alterations in the
arrangement of Si and N atoms in the films. The observed shifts
of the main absorption band, summarized in Table 2, could be
well explained by this effect.
Now we focus our discussion on the feature which appeared
as a “shoulder” to the main absorption band of the SRN films at
1080 cm− 1 after annealing. In order to resolve the absorption
band in the region where the shoulder appeared, we calculated
the second derivative of transmission [26] between 1200 cm− 1
and 950 cm− 1. For the SRN film with Si/N ratio 1.10 annealing
at 950 °C regardless of the duration showed a symmetric peak
located at 1090 cm− 1 in the second derivative (Fig. 3a).
However, for the SRN film with Si/N ratio 1.35 annealed at the
same temperature for 1 h and longer, an extra weaker peak at
1070 cm− 1 was revealed. Annealing of both SRN films at
1100 °C showed both peaks in the second derivative. The
strongest peaks in the second derivative were obtained for the
film with Si/N ratio 1.35 when annealing was performed at
1100 °C for 4 h (Fig. 3b). In the past [27–29] both peaks have
been attributed to the asymmetrical stretching mode of vibration
of Si–O–Si bridges inside SiO2 films. Specifically, the peak
located at 1090 cm− 1 has been attributed to Si–O–Si bridges
located at the boundaries of the SiO2 films while the peak
located at 1070 cm− 1 has been attributed to bridges located at

Fig. 3. Second derivative of transmission in the range where the “shoulder” to the main absorption band appears. (a) Si/N = 1.10 annealed at 950 °C, (b) Si/N = 1.35
annealed at 1100 °C.
9362 V.Em. Vamvakas, S. Gardelis / Surface & Coatings Technology 201 (2007) 9359–9364

1070 cm− 1
the bulk of the films, far away from their boundaries. Therefore,
it is logical to assume that the formation of the “shoulder” at

–
–
y
y
1080 cm− 1 after annealing is due to the formation of Si–O–Si

1090 cm− 1
bridges caused by the partial oxidation of the extra silicon.

4h
When the silicon content was low or the annealing time was

–
–
y
y
short then the oxidation of the films resulted in the formation of

1070 cm− 1
isolated Si–O–Si bridges surrounded by silicon nitride or
silicon clusters. The asymmetrical stretching mode of vibration
–
–
y
y
of these isolated bridges is similar to those boundary bridges
1090 cm− 1

located at the interfaces of SiO2 films thus resulting in the

2h

appearance of the peak at 1090 cm− 1 (Table 3). When annealing

–
–
y
y
1070 cm− 1

time is longer or/and the silicon content of the films is higher,

the possibility of the formation of Si–O–Si bridges surrounded
–
–
y
y

by other Si–O–Si bridges becomes higher. These isolated

1090 cm− 1

bridges which do not “feel” the silicon nitride matrix are

vibrating similarly with those located in the bulk of SiO2 films
1h

thus giving a peak at 1070 cm− 1. However, the origins of the

–
–
y
y
1070 cm− 1

oxygen causing the partial oxidation of these films are not clear.
It is possible that part of this oxygen enters during the
–
–
y
y

deposition of the films, since the same furnace is also used for
1090 cm− 1
1100 °C

the deposition of SiO2 films, although great care was taken to

30 min

avoid any oxygen contamination. We note here that FTIR

–
–
y
y

transmission spectra obtained from stoichiometric silicon

1070 cm− 1

nitride films annealed together with the SRN films did not
reveal the “shoulder”. In addition, second derivative of
–
–
–
y

transmission spectra obtained from the as-grown SRN films

1090 cm− 1

did not clearly reveal the existence of Si–O bonds. It is possible

4h

that the inserted oxygen during deposition is making bonds with

–
–
y
y
1070 cm− 1

the silicon nitride matrix which are infrared inactive. During

Presence/lack of peaks of the 2nd derivative of transmission in the range 1200–950 cm− 1 of silicon nitride films with various stoichiometries

annealing oxygen is redistributed in the silicon nitride films and

–
–
–
y

for the case of SRN films it is easy to oxidize the extra silicon
1090 cm− 1

and form Si–O–Si bridges. This most probably is not hap-

pening for stoichiometric silicon nitride films since before the
2h

–
–
y
y

formation of Si–O–Si bridges a break of Si–N bonds must

1070 cm− 1

occur. This is not thermodynamically favorable at temperatures

All films have a thickness of about 100 nm (y: for presence of the corresponding peak, –: for lack of presence).

as low as 950 °C while temperatures as high as 1100 °C must be

–
–
–
y

considered close to the lowest limit of the oxidation in dry

1090 cm− 1

ambient of silicon nitrides. However, the scope of this discussion

is not to find the origins of the oxygen which is responsible for
1h

–
–
y
y

the oxidation of the films, but it is the fact that SRN films can be
1070 cm− 1

oxidized relatively easy when traces of oxygen are present at

temperatures starting from at least 950 °C.
–
–
–
–

The light emission properties of all films were investigated.

1090 cm− 1
Annealed
950 °C

30 min

The light emission characteristics were mainly sensitive to the

silicon content of the films. Significant improvement in the
–
–
y
y

intensity of the emitted light was realized by post-annealing of

1070 cm− 1

the films at temperatures higher than the growth temperature.

2nd derivative of transmission (1200–950 cm− 1)

After deposition

–
–
–
–

Specifically, the as-grown film with Si/N ratio 1.35 did not give
1090 cm− 1

any detectable luminescence in the region of measurements

between 470 nm and 900 nm. The film with Si/N ratio 1.10
–
–
–
–

demonstrated a broad PL spectrum peaking at 600 nm (Fig. 4).

0.75
0.86
1.10
1.35

The film with Si/N ratio 0.86 showed the most efficient
luminescence peaking at 570 nm. (Fig. 4) We note that the PL
Stoichiometric (Si/N)

spectra obtained from the as-grown films shifted to shorter

wavelengths compared with the indirect band gap of bulk
SRN (Si/N)

silicon (about 1100 nm). A considerable enhancement of the PL

Table 3

peak accompanied by a shift to higher energies with decreasing

 V.Em. Vamvakas, S. Gardelis / Surface & Coatings Technology 201 (2007) 9359–9364
Fig. 4. Photoluminescence (PL) spectra of as-grown and annealed SRN films.
silicon content in the films was observed. We note that de-
creasing silicon content in the films is expected to lead to
formation of silicon clusters of smaller sizes. Considering all of
the above, the most probable explanation for the light emission
from the as-grown films is the quantum confinement of the
carriers recombining in the silicon clusters which may be al-
ready formed during the growth of the films due to the high
temperature of the growth reaction (800 °C). Similar light
emission has been observed in SRN films grown by techniques
other than the one used in this study [15–22]. There is though a
debate as to what is the origin of the light emission. Some
attribute the effect to the quantum confinement of carriers in the
silicon nanocrystals [18, 22] whereas others suggest that the
effect originates from nitrogen-related localized surface states
introduced within the optical gap of silicon nanocrystals [19,
20]. In either case silicon nanocrystals are necessary to confine
the electron and the hole which then recombine radiatively.
All as-grown films were examined for their light emission
properties after annealing. The sample with Si/N ratio 1.35
emitted light only after annealing at 1100 °C in which, as TEM
images demonstrated, silicon nanocrystals of sizes between
1.5 nm and 5 nm were formed [25]. Annealing of the films with
lower Si/N ratio resulted in PL enhancement accompanied by a
shift of the PL peak to shorter wavelengths. Fig. 4 shows this
effect in the case of the sample with Si/N ratio 1.10. This effect
coincided with the appearance of the Si–O–Si vibration modes
in the FTIR spectrum as discussed above in detail. The effect
could be well explained by the enhancement of the localization
of the carriers in the silicon nanocrystals as their size was
reduced due to their oxidation.
4. Conclusions
SRN films with different Si content were prepared by LPCVD
from DCS and NH3 mixtures. Infrared transmission spectra of the
SRN films revealed the existence of an absorption band at about
830 cm− 1 attributed to the Si–N asymmetrical stretching mode.
This band slightly shifted to higher wavenumbers as the silicon
9363
content of the films increased. Annealing at temperatures higher
than the growth temperature caused further shift of the main
absorption band to higher wavenumbers whereas at the same time
a new absorption band at about 1080 cm− 1 appeared as a
“shoulder” to the main absorption band. Calculations of the
second derivative of the “shoulder”, revealed the existence of Si–
O–Si bridges due to partial oxidation of the extra Si from traces of
oxygen which may be inevitably present during annealing. Light
emission properties of the SRN films were sensitive to the Si
content, the annealing temperature and the duration of the
annealing. Enhancement of PL accompanied by a blue shift with
decreasing Si content was observed in the as-grown SRN films.
Similar effects were observed with increasing annealing temper-
ature and annealing time which coincided with the partial oxi-
dation of the Si nanocrystals resulting in a reduction in their sizes.
All these effects could well be attributed to the confinement of the
carriers in the Si nanocrystals which might recombine radiatively
in the Si nanocrystals perhaps via surface states.
References
[1] A.C. Adams, in: S.M. Sze (Ed.), VLSI Technology, 2nd edn, McGraw-Hill,
1988, p. 233, International edition.
[2] F.H.P.M. Habraken, A.E.T. Kuiper, Mater. Sci. Eng. R12 (3) (1994) 123.
[3] D. Davazoglou, Thin Solid Films 437 (2003) 266.
[4] K. Misiakos, E. Tsoi, E. Halmagean, S. Kakabakos, Technical Digest,
International Electron Devices Meeting, 1998, p. 25.
[5] P. Wu, P. Hogrebe, D.W. Grainger, Biosens. Bioelectron. 21 (2006) 1252.
[6] O. Schultz, M. Hofmann, S.W. Glunz, G.P. Willeke, 31st IEEE PVSC
Orlando, Florida, 2005, p. 872.
[7] M. Sekimoto, H. Yoshihara, T. Ohkubo, J. Vac. Sci. Technol. 21 (4) (1982)
1017.
[8] J.G.E. Gardeniers, H.A.C. Tilmans, C.C.G. Visser, J. Vac. Sci. Technol., A
14 (5) (1996) 2879.
[9] E. Cianci, F. Pirola, V. Foglietti, J. Vac. Sci. Technol. B 23 (1) (2005) 168.
[10] M.C. Poon, Y. Gao, T.C.W. Kok, A.M. Myasnikov, H. Wong, Microelectron.
Reliab. 41 (2001) 2071.
[11] J. Chan, H. Wong, M.C. Poon, C.W. Kok, Microelectron. Reliab. 43
(2003) 611.
[12] T.C. Chang, S.T. Yan, P.T. Liu, M.C. Wang, S.M. Sze, Electrochem. Solid-
State Lett. 7 (7) (2004) G138.
[13] K.-H. Wu, H.-C. Chien, C.-C. Chan, T.-S. Chen, C.-H. Kao, IEEE Trans.
Electron. Devices 52 (5) (2005) 987.
[14] S. Choi, H. Yang, M. Chang, S. Baek, H. Hwanga, S. Jeon, J. Kim, C. Kim,
Appl. Phys. Lett. 86 (2005) 251901.
[15] T.-Y. Kim, N.-M. Park, K.-H. Kim, G.Y. Sung, Y.-W. Ok, T.-Y. Seong, C.-J.
Choi, Appl. Phys. Lett. 85 (22) (2004) 5355.
[16] K.S. Cho, N.-M. Park, T.-Y. Kim, K.-H. Kim, G.Y. Sung, J.H. Shin, Appl.
Phys. Lett. 86 (2005) 071909.
[17] L.-Y. Chen, W.-H. Chen, F.C.-N. Hong, Appl. Phys. Lett. 86 (2005)
193506.
[18] T.-W. Kim, C.-H. Cho, B.-H. Kim, S.-J. Park, Appl. Phys. Lett. 88 (2006)
123102.
[19] L. Dal Negro, J.H. Yi, L.C. Kimerling, S. Hamel, A. Williamson, G. Galli,
Appl. Phys. Lett. 88 (2006) 183103.
[20] L. Dal Negro, J.H. Yi, J. Michel, L.C. Kimerling, T.-W.F. Chang, V.
Sukhvatkin, E.H. Sargent, Appl. Phys. Lett. 88 (2006) 223109.
[21] L.B. Ma, R. Song, Y.M. Miao, C.R. Li, Y.Q. Wang, Z.X. Cao, Appl. Phys.
Lett. 88 (2006) 093102.
[22] K. Ma, J.Y. Feng, Z.J. Zhang, Nanotechnology 17 (2006) 4650.
[23] I.P. Herman, Optical Diagnostics for Thin Film Processing, Academic
Press Inc., 1996.
[24] H.R. Philipp, Properties of Silicon, INSPEC The Institution of Electrical
Engineers, 1987, p. 1019, EMIS Datareview RN=16133.
9364 V.Em. Vamvakas, S. Gardelis / Surface & Coatings Technology 201 (2007) 9359–9364

[25] V.Em. Vamvakas, N. Vourdas, S. Gardelis, Microelectron. Reliab. 47 [28] V.Em. Vamvakas, D. Davazoglou, J. Electrochem. Soc. 151 (5) (2004)
(2007) 794. F93.
[26] M. Cardona, in: F. Seitz, D. Turnbull, H. Ehrenreich (Eds.), Modulation [29] V.Em. Vamvakas, D. Davazoglou, J. Vac. Sci. Technol. B 23 (5) (2005)
Spectroscopy, Academic Press, New York, 1969, p. 105. 1956.
[27] D. Davazoglou, V.Em. Vamvakas, J. Electrochem. Soc. 150 (5) (2003)
F90.