PHYSICAL REVIEW B VOLUME 42, NUMBER 5 15 AUGUST 1990-I

Strain-induced quantum confinement of carriers due to extended defects in silicon

H. Wernan*
Center for Quantized Electronic Structures, Uniuersityof California, Santa Barbara, Santa Barbara, California 93106

B. Monemar*
Max Pla-nck Ins-titut fur Festkorperforschung, Heisenbergstrasse1, Postfach 8006 65,
D 7000-Stuttgart 80, Federal Republic of Germany

G. S. Oehrlein and S. J. Jeng

IBM Research Division, Thomas J. Watson Research Center, P. O. Box 218, Yorktown Heights, ¹w York 10598
(Received 6 April 1990)
A recombination mechanism occurring in semiconductors containing extended defects is present-
ed. The model is based on experimental data from hydrogen-plasma-treated silicon, containing ex-
tended defects like platelets. The broad photoluminescence bands from these samples are attributed
to the heavily damaged regions surrounding the platelets, where electrons and holes can be localized
in strain-induced potential wells. From a theoretical estimate it is shown that a moderate compres-
sive strain field surrounding I 1 1 1 I and I 100) platelets is sufficient to explain the experimental data.

I. INTRODUCTION liquid-nitrogen-cooled North Coast EO-817 S Ge detec-

tor.
Low-temperature photoluminescence (PL) studies of High-resolution electron microscopy was performed on
defects in silicon have become a field of great interest a JEOL 200 CX microscope with a resolution of 2.5 A.
during the past 15 years, as recently reviewed by Davies. ' Both (110) cross-sectional and (111) plan-view specimens
Most of the work has been concentrated on bound- were prepared for the TEM study. Cross-sectional sam-
exciton spectra of various impurities in the crystal, intro- ples were ion-milled with an Ar beam at liquid-nitrogen
duced both intentionally (by doping) or nonintentionally temperature.
(process induced). The PL from these centers usually A variety of different hydrogen- and deuterium-
gives rise to very sharp PL lines from which the proper- plasma-treated silicon samples, including subsequent
ties of the defects can be analyzed in detail via perturba- isochronal annealing, have been studied. Other details of
tion spectroscopy. However, in some cases broad the experimental setups and sample preparations we used
featureless PL bands are observed, which have been al- can be found elsewhere. '
most neglected in previous work. It is the purpose of
this paper to present a new model which can explain the III. EXPERIMENTAL RESULTS
origin of these broad PL bands. The model is based on
the effects of the local strain fields that surround extend- A typical PL spectrum that will be the basis for the
ed defects, as we tentatively suggested recently. discussion of our model is shown in Fig. 1. The spectrum
These
broad PL bands are commonly observed only in samples
WAVELENGTH (pm)
where more extended defects are seen. This includes
1.7 1.6 1.5 1.4 1.3 1.2
oxygen-precipitated, ' antimony-precipitated, and i I I I I

hydrogen-plasma-treated silicon. The model presented Si:B

T=2K 10x
in this paper is based on experimental data from tD
H2 plasma, 250'C
hydrogen-plasma-treated silicon, where the geometry and C
dimensions of the extended defects (platelets, gas bubbles) tD
C3
are well known from transmission electron microscopy C
tD
C3
(TEM). It has been shown that these platelets are com- V)
CD
C:
0.94eV
monly occurring as I 111I planar defects with an exten- E
0.85eV BTA
sion of about 100 A. O
Ct I I

0 0.8 0.9 1.0 1.1

II. EXPERIMENT PHOTON ENERGY (eV)

The PL spectra were taken at temperatures from 2 to FIG. 1. PL spectrum at 2 K of a boron-doped Cz-silicon
100 K, excited with the 6471-A line from a Kr+-ion laser sample plasma-treated at 250 C in a 400-mTorr hydrogen plas-
with a power density of 2 W/cm . The luminescence was ma for 3 h. The PL bands at 0.94 and 0.85 eV are due to the
dispersed with a SPEX Industries Inc. , model 1404 0.85- etching treatment, while the PL peaks between 1.2 and 1.0 eV
m double-grating spectrometer, and detected with a are due to different replicas of the boron-bound exciton.

42 3109 1990 The American Physical Society

3110 H. WEMAN, B. MONEMAR, 6. S. OEHRLEIN, AND S. J. JENG

related defects in the near-surface region, is based on the

fact that the silicon lattice surrounding these extended
defects is highly strained. If we consider, e.g. , a platelet
defect, as shown in Fig. 2(b), it has been shown that the
hydrogen-stabilized platelet separates the silicon bound-
ary layer by a distance exceeding the normal lattice dis-
tance by about 20 —30%.
This means that there is a strong compressive strain
field perpendicular to the platelet, so that the lattice con-
~(!(! stant could be considerably reduced in this direction.
I II I lk 'kjf 'Q 11 ~

The strain field has an extension of about 100 A, as

FIG. 2. (a) (110) cross-sectional lattice image and (b) a high-
resolution lattice image of a {111{hydrogen platelet of a Si
sample treated as described in Fig. 1.
is taken at 2 K of a boron-doped, (100)-oriented, 10-
Oem, Czochralski (Cz) -grown silicon sample plasma-
treated at 250'C in a 400-mTorr hydrogen plasma for 3
h. The sample was excited with the 6471-A line from a
Kr+-ion laser with a power of about 2 W/cm . The
broad PL band peaking at 0.94 eV with a half-width of 30
meV [full width at half maximum (FWHM)], with addi-
judged from the TEM data [Fig. 2(b)]. This compressive
strain field will lead to a considerable reduction of the
band gap and then to a localized "quantum-well"
confinement of both electrons and holes, as will be shown
in detail below.
In order to make quantitative estimates of the local
shifts in the valence and conduction bands around a
platelet defect, some simplifying assumptions are made.
The strain-induced change in the lattice constant perpen-
dicular to the plane of the platelet (a~) is supposed to be
much larger than the change parallel to the platelet (ai ),
and the latter is therefore neglected. From the known
values of the deformation potentials in silicon, one can es-
timate the shift of both the valence-band top and the
lowest conduction-band minima, and, in addition, the
contribution to the average band-gap shift from the hy-
drostatic components of the strain field. ' For the up-
shift of the valence band with respect to the weighted
average due to strain splitting, one can derive an expres-
sion like
AE, = ,'6o+ ,'5E— , )']'~', —
+—,[b (')+—5o5E—+'(5E
'

tional weak structure centered around 0.85 eV, is due to

the plasma treatment of the sample, while the PL peaks
valid for a uniaxial stress along [001] or [111]. Here, '
Ap is the spin-orbit splitting at 1 z~ in unstrained silicon
between 1.2 and 1.0 eV are due to different replicas of the
boron-bound exciton. The broad PL bands were found
(bo-0. 044 eV) and 5E is the linear component of the
strain-induced splitting of the multiplet of the valence-
to disappear after a chemical etch removing about 0.5
band top. For {111{-oriented platelets, the splitting
pm.
The (110) cross-sectional lattice image of a similarly 5E!,»! can be expressed as
treated Si sample is shown in Fig. 2(a). It shows a high 5E(&&&! 2+3d (2)
density of {111] planar defects and some {100) planar
defects that are distributed from the Si surface to a depth where d is the appropriate deformation-potential con-
of about 0.3 pm. The lattice strain associated with this stant (d= — 4. 85 eV, Ref. 11) and the component e„of
type of defect suggests that the defect is a hydrogen-
stabilized platelet. Secondary-ion mass spectrometry
(SIMS) depth profiles of similarly deuterium-plasma-
e„-
the strain tensor in this case may be approximated by
'
—, b, a~/ao,
'
where ha~ is the change of the lattice
parameter perpendicular to the platelet and ap denotes
treated Si show that the average deuterium concentration the lattice parameter for unstrained silicon (5.43 A).
is higher than 10' crn within the first half- Similarly, for { 100{-oriented platelets, 5E!No! is given by
micrometer.
5E!too~ =2b(ezra e~x ) (3)
IV. DISCUSSION
where b is the appropriate deformation-potential pararne-
W'e have previously shown that our data are not con- ter (b = —2. 1 eV, Ref. 11), and in this case
sistent with any conventional recombination model sug-
gested for the broad PL bands, such. as free-to-bound,
e„-0,e„-ha&/ap. '
For the conduction band there is no splitting in first or-
donor-acceptor —pair, or excitonic recombinations (in- der of the lowest b, conduction band for {111]-oriented
cluding excitonic-phonon coupling to local modes), or an- platelets, while for {100j orientation there will be a
nihilation of free excitons by inelastic scattering. ' Our downward shift of the magnitude
model, which can explain the behavior of the broad PL
bands (as shown in Fig. 1) associated with extended H- (4)
42 STRAIN-INDUCED QUANTUM CONFINEMENT OF CARRIERS. . .
where, again, =„
is the appropriate deformation-potential
constant (:-„-8.
6 eV, Ref. 11}; e„„-0 E„—
and ha~/ao.
In addition, there is an average hydrostatic change EEg
in the energy gap given by
hE =+I e,
where I is theunit dyadic tensor, e is the strain tensor,
" experimental spectrum in Fig. 1, which is from a sample
and a is given as 1. 50+0. 3 eV. In Table I the calculated
up-shifts of the valence band, the down-shifts of the con-
duction band, and the hydrostatic and total changes of
the band gap are shown for a maximum strain b, a~/ao of
1%, 3%, and 5%, respectively, in the [111] and [100]
directions.
The values in Table I serve to demonstrate the main
features of the proposed model for the electronic struc-
ture of the hydrogen-induced extended defects in silicon.
Clearly, for a compressive stress field the valence band
will be pushed up, while the conduction band will come
down, compared to unstrained silicon. (The strain-field-
induced reduction of the band gap will also be much
larger for [100]- than [111I-oriented platelets, for the
same perpendicular deformation, since the conduction
band is only affected by the hydrostatic change of the
band gap in the [111] direction. ) This means that there
will be notches in both band edges at the interface to-
wards the platelets, so that both electrons and holes can
be localized in the same region, as shown in Fig. 3. This
is in contrast to the case of a heterostructure interface,
where typically only one carrier can be localized. The ex-
tent of the potential notches is connected to the extent of
the strain field. We have not attempted any self-
consistent calculation of the spatial variation of this
strain field, but the contrast observed in TEM pictures of
these platelets, Fig. 2(b), indicates an extension of about
100 A. This rather wide potential may give rise to one or
more bound levels (depending on the depth and length of
the notches} for electrons and holes, respectively, at rath-
er small distances 5, and 5& from the respective band
edges (Fig. 3). Since Si has an indirect band gap, the ob-
served recombination process is supposed to be a
phonon-assisted transition between electrons and holes
both localized in the potential "well" close to the inter-
face. In Si the dominating phonon replica is the
transverse-optical (TO} mode. The emission would then
Platelet~ strained unstrained
Si Si
Ec
AF.
Eg
AF. v
V ~+~ h
Ev
FIG. 3. Strain-induced quantum-confinement model describ-
ing the origin of the broad PL bands.
3111
be expected to peak at
hv=E —E (TO) E, +DE„+DE)+(b, , +Eh
(b— ),
(6)
(5) with the values E =1.1695 eV (at 2 K), E~(TO) = 0.058
eV, and 6,+hz -0.05 eV. Upon comparison with the
shown to contain a high density of [111] platelets and
some [100I platelets, we may associate the strong PL
band peaking around 0.94 eV to [111I-oriented platelets
and the weak PL band around 0.85 eV to [100]-oriented
platelets. For a [111] ([100]) platelet, the emission
would then be expected to peak at around 0.94 eV (0.85
eV) for a maximum value of Aaj /ao of about 3.1%
(2.7%) to be consistent with this model.
For the [111]-oriented platelet the valence-band top
would be raised by about 0. 175 eV compared to un-
strained material, while the conduction band would be
lowered by an unknown partition of EEg, which is about
46 meV in this case. From the temperature dependence
of the 0.94-eV band, a binding energy of 35 meV was es-
timated for the loosely bound particle, giving a binding
energy of about 137 meV for the tightly bound particle.
This fits very well with the strain distribution surround-
ing a I 111) platelet if one assumes that most of the hy-
drostatic change is a lowering of the conduction band.
From the fit of the PL band for the I100I-oriented
platelets, the upward shift EE„I, is about 0. 116 eV, and
OOI
the 5 conduction band is lowered by a similar amount,
-0. 155 eV, in this case (in addition to the hydrostatic
shifts of 40 meV). This is also consistent with the
thermal activation energy of the 0.85-eV band, which was
determined to be around 110 meV, which is the binding
energy of the loosely bound particle, giving a binding en-
'
ergy of about 152 meV for the tightly bound particle.
Unfortunately, the TEM data available are not
sufficiently accurate to resolve the interplanar compres-
sion of the Si planes nearest to the platelets. It is, howev-
er, of a reasonable magnitude, if it is assumed that the ob-
served total strain is accommodated gradually over the
strained region (i.e., the change in a~ is gradual).
Other broad PL bands observed at different energies
and with varying half-widths might be accounted for by
other hydrogen-induced inclusions (e.g. , the gas bubbles)
of different geometry and size. The latter would be more
difficult to model exactly, but the above analysis shows
that it is sufficient to have a compressive stress field in
some region around such a defect to achieve localization
of both electrons and holes in that region.
One should also keep in mind a number of effects that
would serve to broaden the observed spectra. It is well
known from studies of electronic levels in two-
dimensional potentials in heterostructures that the local-
ized levels are considerably broadened. ' In addition,
and perhaps more importantly, we have to assume that
the ensemble of platelets in a sample exhibits some varia-
tions in size, in shape, and, consequently, in strain-field
profiles, making the potentials vary among the platelets.
Further, overlap between different types of hydrogen-
related defects will also contribute to the observed
3112 H. WEMAN, B. MONEMAR, G. S. OEHRLEIN, AND S. J. JENG 42

TABLE I. Calculated values for the up-shifts of the valence band, EE„
the down-shifts of the con-
duction band, AE„and the hydrostatic change, EEg, and the total change, EEg t t of the band gap for
various values of the strain ha~/ao in the [111]and [100] directions.

Aaj /a0 ~EU I 100 ) ~EutlllI ~Ec ~

100I ~Ec I 111 I aE,0 ~Eg tot I 100 j ~Eg tot t 111 I
(%%uo) (meV) (meV) {meV) (meV) {meV) (meV) (meV)

47 60 57 15 119 75
128 170 172 45 345 215
211 281 287 75 573 356

broadening. The PL intensity from this type of recom-
bination is very efficient, since, firstly, the density of
platelets is very high in the near-surface region [about
10' cm, as judged from Fig. 2(a)], and, secondly, since
this region is highly passivated by the hydrogen, other
competing radiative as well as nonradiative recombina-
tion channels are quenched. It should be noted that this
recombination model is not affected by the passivation
effect of hydrogen.
We believe that this strain-induced confinement of car-
riers is also the origin of the broad PL bands observed in
oxygen-precipitated Si (Ref. 4) and antimony-precipitated
Si (Ref. 3). This recombination mechanism should be val-
id for other semiconductors as well, where local strain
fields are present, since the model is not related to the
electrical potentials of the defects. For instance, very
similar broad PL bands have also been observed in
hydrogen-plasma-treated GaAs. ' It is also possible that
the broad PL bands observed in strain-adjusted Si/Ge su-
perlattices' can be explained by the same recombination
model. It has recently been shown that carriers can be
confined to quantum wires and boxes by deliberately
creating large inhomogeneous strain patterns in quantum
wells. '
V. SUMMARY
In summary, we have presented a new recombination
mechanism occurring in semiconductors containing ex-
tended defects which is based on experimental data from
plasma-treated Si, where I 1 1 1 I and I IOOJ platelets have
been observed by TEM. The observed broad PL bands
are attributed to the strain surrounding these defects,
where electrons and holes can be localized in potential
wells. A simple theoretical estimate has been used to
show that the compressive strain field which surrounds
these platelets and reduces the Si lattice constant normal
to the plane of the platelet up to a maximum of about 3%%uo
is sufficient to locally reduce the band gap by as much as
0.3 eV, consistent with our data.

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