Solid-StoreHecrronics Vol. 41, No. 6, pp.

887-893, 1997
0 1997ElsevierScience Ltd. All rights reserved
Pergamon Printed in Great Britain
PII: SOO38-1101(97)00025-7 0038-I101197 $17.00+ 0.00

ELECTROLUMINESCENCE OF MOS CAPACITORS WITH

Si-IMPLANTED SiOz
T. MATSUDA’, M. NISHIO’, T. OHZONE’ and H. HOR12
‘Department of Electronics and Informatics, Toyama Prefectural University, Kurokawa, Kosugi-Machi,
Imizu-gun, Toyama 939-03, Japan
*Semiconductor Research Center, Matsushita Electric Ind. Co. Ltd. Yagumonaka-machi, Moriguchi.
Osaka 570, Japan

(Received 24 Ju1.v 1996: in revised form 14 November 1996)

Abstract-Electroluminescence (EL) characteristics of n+-polysilicon MOS capacitors with 50 nm

Si-implanted SiO2 were measured. The EL intensity is almost proportional to the gate current, and the
EL efficiency is about S&70 times larger than that of a MOS capacitor without Si-implantation. Although
the EL spectra of MOS capacitors have a broad peak around 650 nm regardless of the Si-implantation,
only the EL intensity of Si-implanted MOS capacitors increases gradually below 500 nm. The latter may
be caused by radiative electron capture into two kinds of SiOztrap levels, 2.g2.5 and 3.0 eV below the
conduction band of SiO2. 0 1997 Elsevier Science Ltd

1. INTRODUCTION junctions[l9] has been discussed for display device

Since the observation of room-temperature photo-
luminescence (PL) in porous silicon (PS) with
nanometer-size crystals[l], electroluminescence (EL)
PS-devices with electrodes employing Al/Au/Q/IT0
films[2], SiC[3], polymer contacts[45] and electro-
lytes[6] were developed for practical use in opto-
electronics. However many problems must be
overcome for practical applications of EL PS-devices;
the instability of light emission in an ambient, the
strong dependence on the fabrication conditions,
fragile mechanical properties, the difficulty to form
electrodes at the rough PS surface with good
current-injection efficiency, and finally the inferior
process compatibility with Si LSI.
Recently, a number of alternative synthesis
methods of nanocrystals was proposed; nanocrys-
talline Si film crystallized from amorphous Si[7],
Ge-crystal-doped silica glass by sol-gel method[8],
SiOrdoped Si films[9], nanocrystals imbedded in
oxide[ 10-l 31, or ion-implantation of Si[ 14-l 51 and
Ge[ 161 into Si02. The ion-implantation approach
seems quite promising, because of the controllability
of nanocrystal formation, well passivation from the
external ambient and excellent compatibility with
Si LSI processes are satisfied. However, the ion-
implanted SiO2 films are estimated by PL methods.
Only the EL characteristics of Ge-implanted p+-
polysilicon/Si02/Si structuresI 161 have been reported
so far. In contrast, EL effects from MOS capacitors
with thermally grown SiOl under Fowler-Nordheim
tunnel conditions have been measured for reliability
analysis and characterization of SiOr film[ 17-181.
Further, EL photoemission from MOS tunnel
application.
Here the EL intensity and spectrum from
n+-polysilicon MOS capacitors with 50 nm Si-
implanted Si02 were measured and compared with
published ELjPL spectra to discuss the possibility
of optoelectronic device application. The EL MOS
capacitors have process compatibility with Si-LSI
as well as EEPROM/NVRAM devices with Si-
implanted Si02[20,21].
2. EXPERIMENTAL
2.1. MOS capacitors
Figure l(a) shows a cross-sectional view of a
MOS capacitor with Si-implanted gate-Si02. The
process sequence of the MOS capacitor was the
same as for the conventional n-MOSFET with a
single polysilicon-gate except for the additional
Si-implantation after the gate oxidation[20]. The
substrate is p-type silicon of 1 x 1015cm-‘. The MOS
capacitors are isolated by a LOCOS process with
a field oxide of 0.6 pm. The channel stop doping of
about 6 x 10’”cm-’ is formed to a depth of 0.45 pm
under the field oxide. Boron channel-implantation
of 6 x 10” cm-’ at 40 keV is performed before
gate oxidation. The gate oxide of 50 nm is grown
thermally and then Si-ions are implanted into the
gate oxide at various implantation conditions. After
phosphorous doped n+-polysilicon gates of 0.35 pm
thickness are patterned, n+-regions surrounding the
MOS capacitors for inversion measurements are
formed by a self-aligned As-implantation with a dose
of 6 x 10” cm-* at 80 keV to a final junction depth
of 0.20 pm. Then CVD-Si02 film is deposited and

887
888 T. Matsuda et al.

etched to form contact windows. Finally aluminum 1 x lO”‘cm- with energies of 20 keV and 50 keV.
interconnections are formed and sintered. The total Since the Rp at 20 keV implantation locates closer
thermal annealing after Si-implantation is 900°C for to the polysilicon-SiO* interface, Si-atoms scarcely
30 min in Nz ambient. (i.e.; less than l/l00 of the peak %-concentration)
Five kinds of Si-implanted MOS capacitors were exist near the SiOrSi interface. However, the Rp at
fabricated as shown in Fig. I(b). Three samples 50 keV implantation locates around the SiO*-Si
(hereafter called # 25 1, 2 and 3) have gate-ho2 with interface. Si-implantation of 3 x lOI crne2 at 25 keV
Si-doses of ( 1, 2 and 3) x 10” cm -’ at an energy of represents about 15% of off-stoichiometric Si in
25 keV at which the projected range Rp locates the SiOz. A MOS capacitor without Si-implantation
around the center of the gate-SiOz and about l/l0 was also fabricated as a reference device (called #O).
of the peak Si-concentration is distributed near The sample #0 was processed in the same way as
the SiOz-Si interface. The other two samples (called the other Si-implanted samples except implantation
#20-l and #50-l ) were implanted to a dose of step.

\ Channel-Stop Dope
Si-Implanted
\ 4x10’6 cm-3
Gate402 (50nm) \ \
// ‘\
‘.
_.’ .___-_--

‘r p-9 ; lx1015cm-3

Gate-SiOs ’ Si-Substrate
#25-3 !
I i

Depth x (nm)

Fig. 1. (a) A cross-sectional view of a test MOS capacitor with S&implanted SiO2, and (b) implanted
Si-profiles calculated by the LSS theory.
 Electroluminescence of MOS capacitors
MOS capacitors of 0.48 mm2 for accumulation
measurements (i.e.; under negative gate voltages
- VG) are not surrounded by the n+-regions, while
those of 0.13 mm’ for inversion measurements (i.e.;
under positive gate voltages + VG)are surrounded by
n+-regions to form inversion layers under the MOS
capacitors.
2.2. Measurement system
Figure 2 shows an ELjPL measurement system
to analyze both images and spectra. The system is
set in the light-tight enclosure. A device under test
(DUT) fabricated in a six-inch wafer is set on a
micro-manipulator wafer prober. Current/voltage are
supplied to DUT from a power supply unit. UV-light
generated by Xe-short-arc-lamp through a band-pass
filter is used as a PL excitation light source, and
illuminates DUT through an optical fiber. An image
of the reflected light from DUT illuminated by an
external light source and the EL/PL images are
magnified by an optical microscope. A variety of long
working-distance objective-lenses and relay-lenses
provide magnification from 5 x to 2500 x . An optical
band-pass filter and a neutral density (ND) filter can
be inserted in series between the optical microscope
and the CCD camera. The cooled CCD camera
system is CH250 with a TEK512CB/AR CCD
imager manufactured by PHOTOMETRICS Ltd.
A stabilized temperature in the Peltier cooled
camera head is -45°C. TEK512 CCD is a backside
illuminated, four phase and full frame CCD with
512 x 512 pixels of 27 x 27 pm pixel size. The ELjPL
emitting position can be determined by a resolution
of about 2.7 pm/pixel at the microscope magnifi-
cation of 10 x used in the present measurements. A
typical dark current and a linear full well capacity
under MPP mode operation are about 0.6 electrons/s
and 295 k electrons, respectively. The ELjPL image
at a specific wavelength can be measured by inserting
( Image Measurement )
*.................................,
Optical
~j~{~~...~~~~~~~
;.................................;
Light-light Enclosure
Fig. 2. Schematic diagram of the EL/PL image and spectrum measurement-system.
889
the band-pass filter. When the band-pass filter is
not used, the EL/PL image from 400 to 900 nm is
measured. The shortest and the longest wavelengths
are limited by the spectrum responses of the
microscope and the CCD imager, respectively.
For the EL/PL spectra measurements, a mono-
chromator is inserted between the optical microscope
and the CCD camera through optical fibers. A cut-off
filter of PL excitation light is inserted between the
optical fiber and the monochromator for rejecting
the influence of the excitation light as well as
the second harmonics. The 0.3 m monochromator
(MC-30N with 150 groves/mm blazed at 500 nm) was
manufactured for Ritsuu Ltd. The measurable
spectrum ranges from 400 to 900 nm with a spectral
resolution less than 1.0 nm. Since ELjPL spectrum
wavelength width of 300 nm is measured at once,
the EL/PL spectrum change during the measurement
can be reduced by the short spectra measurement
time.
By taking a background measurement before
DUT was biased or excited, noise data caused by
the light leaks and the system noise were stored in the
image processor. In the next place, reflected light
image and/or EL/PL data were measured. The
signal-to-noise ratio was substantially improved by
subtracting the background noise from the measured
data. The EL/PL spectra data were corrected for the
wavelength responses of the measurement system.
As the EL MOS capacitors used in our experiments
were covered by the heavily doped n+-polysilicon
film, the measured EL spectra were also corrected
by the absorption coefficient data of the heavily
phosphorous-doped polysilicon film in the wave-
length range from 0.45 to 1.0 pm[22]. The total
correction coefficient by which the spectra data was
multiplied is shown in Fig. 3. All measured EL
intensity data were multiplied by the total correction
coefficient before being plotted in the figures.
f PL Excitation Source f
890 T. Matsuda el al.

3. RESULTS

EL intensity-distribution images were measured

1 0.' -#25-2
by supplying a constant gate current JG using a semi- -125.3
conductor parameter analyzer HP4145B. -&(+JG) n^ -#20-l
g 1o-2 -+-650-l
currents were supplied to the gate while keeping the
a_
p-Si substrate (both the p-Si substrate and the
0 1 o.3
n+-region surrounding the MOS capacitor) at 0 V for 7

accumulation (inversion) measurements.

+JG currents were first supplied from 10m6A cmM2,
and were stepped up at a rate of (1, 2, 4, 6) x
IO-” A cm-’ until the oxide breakdown. EL intensity
can be measured over 10e5 A cm-’ at an exposure
time of 3 min for the CCD camera. When high Jc was
supplied, the EL signal sometimes becomes over the
full well capacity of the CCD imager. In such cases,
the exposure time was shortened according to the
EL intensity. As Vc decreased rapidly in a relatively
short time and then saturated under the constant JG
for the Si-implanted MOS capacitors[23], the EL
measurements were started after 1 min later from Jo -#25-l
-#25-2
supply to obtain EL intensities at the saturated VG -#25-3
Figure 4(a) shows Jc vs the saturated Vc character-
istics of various MOS capacitors under accumulation.
The JG-vG curves under both accumulation and
inversion conditions were well consistent with those -Jo (A/cm’)
measured for the samples before stress supply[23]. (b)
The EL intensity measured without the optical Fig. 4. (a) Current-voltage characteristics and (b) EL
band-pass filter under accumulation vs JG is shown intensity vs current characteristics under accumulation.
in Fig. 4(b). The EL intensity data were obtained
by summing the photon counts over the uniform
photoemission area a little distant from the LOCOS be measured to the high current regions. EL emission
edge, because the EL intensity-images near the efficiency of Si-implanted MOS capacitors was about
LOCOS edge sometimes become non-uniform 50-70 times larger than that of #O. EL character-
because of the high Jc currents. The unit of EL istics under inversion showed a little scattered curves
intensity was normalized to photon counts per cm* in comparison with the accumulation data. However,
for an exposure time of 3 min, and thus EL intensities the EL intensities for the same JG were similar to the
for all samples including in both accumulation and accumulation data.
inversion can be comparatively discussed. Concern- Figure 5(a) shows EL spectra of Si-implanted MOS
ing EL characteristics under accumulation. EL capacitors under accumulation at -JG = lO-2 A
intensities increase proportionally to -JG in low cm-l. EL spectrum of #0 at -& = 10-j A crne2 is
currents and then gradually saturate around also shown. The similar curves were also measured
lo-* A cm-’ except #0 and #25-l which could not under inversion. The periodic patterns observed in
EL spectra independently of samples may be caused
by the interference of the reflected light at the

0
‘03m
-
surface and the bottom of n+-polysilicon gate similar
to the PL spectra of Si-implanted thick Si02[14].
The intervals of the interference pattern caused by the

i:::;yL&y
;
.g

multiple reflection is given as[24]:

2?IYf=(l/& - l/I,)-‘, (1)

where n is the refractive index and d is the thickness
6
0
_ \ ‘. of the polysilicon film (0.35 pm). 1, and I2 (I, > 1,)
*-. 91~_P_olyrlllcon are the peak wavelengths observed in the spectra.
,90& I I I I I I I I-il,-r+..,-.. 1 C. III,I From three peaks observed in the wavelength range
400 500 600 700 800 900 1000
Wavelength A (nm) from 500 to 900 nm, average II value was estimated
as about 5.1 which was in good agreement with
Fig. 3. Total correction coefficient used to multiply the
measured spectrum data. Correction coefficients of the n = 4.8-3.7 (2 = 450-750 nm) for heavily phospho-
measurement system and the n+-polysilicon gate of 0.35 pm rous-implanted polysilicon film[22]. In contrast, an
are also shown. interval of the interference pattern caused by the
 Electroluminescence of MOS capacitors 891

Photon Energy (eV)

gate oxide of 50 nm is estimated as 300-700 nm in
4.03.5 3.0 2.5 2.0
I = 400-800 nm by assuming n = 1.46 for Si02[25].
Although the optical calculation of the multi-layer
system including polysilicon and SiO, is necessary
for more accuracy, it can be concluded that the
interference patterns are mainly caused by the c
C
polysilicon gate. *loa
Jc dependence of EL spectra under accumulation Z
for #25-2 is shown in Fig. 5(b). Nearly the same s
characteristics were obtained for # 50-l. The periodic E

patterns were also observed independently from d -

Jc. The solid lines show the corrected spectra by
taking the average of periodic patterns in the curves. %oo 400 500 600 700 800 900 IO00
Wavelength k (nm)
Emission with short wavelength range is dominant in
lower -JG, and emission with middle wavelength (a)
range around 650 nm becomes large as -Jc Photon Energy (eV)
increases. Those data suggest that the EL spectrum
(i.e., EL color) as well as EL intensity can be
controlled by changing JG.
Figure 6(a) shows the corrected spectra of various
Si-implanted MOS capacitors under accumulation at

!;;fa ,,,,,
-& = lo-* A cm-2. The previous studies of ELjPL
spectra from various Si02 films are shown in
Fig. 6(b). The proposed photoemission mechanisms

Photon Energy (eV)

,,,) 1
3.0 2.5 2.0 1.5
300 400 500 600 700 800 900 1000
10’1~~~~1~~~~1 0 1 1 I 1
(Accumuldon) -%o Wavelength )i (nm)
g - -Jo =l~zAlcm~ -#25-2' (b)
SIdF -625-3
-820-l Fig. 6. (a) Measured EL spectra under accumulation
c - -#50-l in comparison with (b) previous studies of ELjPL spectra.
L - (EL spectra) Ref. [12]; Transparent Au/sputter deposited
&ldF S&rich SiOz (3-5 nm)/p-Si. Ref. [I’/]; n+-polysilicon/thermal
:: - SiO? (20 nm)/p-Si. Ref. [18]; n+-polysilicon/thermal SiO?
e! - 1 (24 nm)/p- and n-Si. (PL spectra) Ref. [14]; thermal SiOz

PJ; ,,.( I ,,,,,,,,,,,,,,,,,,,,,, 1 (1.75 pm) with S&implantation

[I 100°C anneal]. Ref. [IS-(a)(b)];
with Si-implantation
(2 x 10” cm-?, I MeV)/p-Si
thermal SiO? (0.43 pm)
(l(3) x 10” cm-?, 160 keV)/p-Si
[lOOWC anneal].
500 600 700 800 900 1000
Wavelength h (nm)
(a)

Photon Energy (eV) were diverging and sometimes contradictory as

_ 3.0 2.5 2.0 1.5 described in the following. The peaks around 500 nm
were explained by radiative electron capture into
: (Accumulation) -1x10~zA/cm2 _
traps in SiOJ18], and quantum confinement in very
e5x10~3A/cm
small Si nanocrystals or excitonic recombination
/cm' 3
in chains of Si atoms[l5]. The peaks around
(600-700 nm) were attributed to electron/hole
recombination in the luminescence center of the
Si02 near Si nanocrystal-Si02 interface[ 12,141, or
recombination of high-energy electrons with impact-
generated holes in the n+-polysilicon film[ 17,261.
The red-light PL emission from the sample labeled
Ref. [15-b] was proposed to be quantum confinement
Wavelength 1 (nm) in Si nanocrystals[ 151.
(b) The #0 sample shows a broad peak around
Fig. 5. (a) EL spectra under accumulation at
650 nm. However, our data of Si-implanted MOS
--JG = 10m2 A cme2 for various samples and (b) EL spectra capacitors are quite different from the previous
at various currents under accumulation for #25-2. ELjPL data. EL spectra showed a characteristic
892 T. Matsuda et al.
curve independently of the Si-implantation con-
ditions; a broad peak around 650 nm as observed in
#0 sample and a gradually increasing region below
500 nm, though detailed EL spectra and intensities
are a little different for each sample.
4. DISCUSSION
Different Si-implantation parameters have clear
influence on the I-V characteristics as shown in
Fig. 4(a). Type and density of traps generated by
Si-implantation may affect the I-V characteristics.
Those results were discussed in Ref. [23]. In contrast,
for the order of lO’“cm-’ dose, the Si-implantation
parameters do not much affect the EL intensity of
Si-implanted samples as shown in Fig. 4(b). Although
the EL intensity for the gate current is independent
from the implantation parameters, these samples
require different gate voltages for the currents caused
by the difference of the I-V characteristics. The EL
intensity under accumulation depends linearly on the
gate current. It suggests that one type of carriers
(electrons in this case) has to be injected from the
gate. The difference between EL spectra of devices
with and without Si-implantation as shown in
Fig. 6(a) indicates that Si-implantation increases the
same kind of traps in unimplanted SiO, over ten times
and generates new traps which locate deeper below
the conduction band of SiOz than the former traps.
The quantity and the energy level from the
conduction band of SiOz for the new traps generated
by various Si-implantation conditions with doeses
over 1 x lOI cm-” seem to be nearly equal because
EL intensity and spectrum are almost independent on
the Si-implantation parameters as shown in Figs. 4(b)
and 6(a), respectively.
The proposed photoemission mechanisms for
accumulation are illustrated in the energy band
diagram of n+-polysilicon/SiOJp-Si structure[27]
as shown in Fig. 7. The broad 650 nm (hv = I .9 eV)
peak observed in all MOS capacitors may be
explained by hv, emission mechanism (i.e., the
radiative electron capture into traps which tend to be
between Et = 2.0 and 2.5 eV (i = 620-500 nm) below
the conduction band of SiOz[18]). However. the
gradually increasing region below 500 nm can be
attributed to another hv, mechanism (hv; in Fig. 7)
(i.e., the radiative electron capture into traps
generated by Si-implantation located at E; 3.0 eV
(A’ 410 nm)[28]), or hvl mechanism (i.e., recombina-
tion of injected high-energy electrons with holes in
accumulated p-Si surface[26]). The hv; mechanism
seems more reasonable than the hvl mechanism,
because the gradually increasing region is not
observed in #0 and further photons emitted from the
hv2 mechanism may have energies higher than 4.3 eV
(i’ 290 nm) which could not be observed in our
measurement system.
The EL intensity vs gate current characteristics
shown in Fig. 4(b) may be explained as follows.
n+ -polysilicon SiO2
gate n
EC
EF
EV
Fig. 7. Energy band diagram illustrating photon emissions
from MOS capacitors under accumulation. EC, EV and EF
refer to conduction band, valence band and the Fermi level
energy, respectively. E, (C) refers to the trap energy level in
Si02 below the SiO, conduction band. /WI (hv;) and hvz
illustrate photon emissions from electron capture at the
traps and from recombination of high-energy electrons with
accumulated holes in Si-substrate, respectively. Energy
values are indicated in eV.
Under low gate current, the injected electrons are
captured effectively into the large quantity of traps in
SiO, and thus the EL intensity is determined by the
number of electrons (i.e., EL intensity increases
linearly on the gate current). However, the radiative
electron capture into the traps is limited by the
quantity of traps when the number of injected
electrons become extremely large and then some
electrons flow out into the Si-substrate without
radiative recombination resulting in EL saturation at
high current densities.
Our data showed that Si-implanted MOS
capacitors had a possibility to emit much stronger
visible EL light than the MOS capacitors without
Si-implantation, and further to emit strong UV-light
less than 450 nm. Number of traps must be increased
and be more uniformly distributed in Si02 layer to
improve the photoemission efficiency. More exper-
imental works are necessary for further detailed
understanding in the photoemission mechanisms in
Si-implanted Si02. It is also effective td investigate
other implantation atoms which have higher radiative
recombination rate than Si atoms and energy
levels corresponding to a wavelength desired for
optoelectronic device applications.
It may be useful to investigate MOS capacitors
within a thin n+-polysilicon film less than 50 nm,
because the absorption coefficient of the n+-
polysilicon film increases steeply in wavelength range
less than 500 nm resulting in large spectrum error.
Further, the interference interval in the spectrum may
 Electroluminescence of MOS capacitors 893

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5. CONCLUSION
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