Surface Science 513 (2002) 475–484

www.elsevier.com/locate/susc

C incorporation and segregation during Si1
y Cy =Si(0 0 1)

gas-source molecular beam epitaxy from Si2H6 and CH3SiH3
Y.L. Foo, K.A. Bratland, B. Cho, J.A.N.T. Soares, P. Desjardins, J.E. Greene *

Frederick Seitz Materials Research Laboratory and the Materials Science Department, University of Illinois, 104 S Goodwin Avenue,
Urbana, IL 61801, USA
Received 12 December 2001; accepted for publication 23 April 2002

Abstract
We have used in situ D2 temperature-programmed desorption (TPD) to probe C incorporation and surface segre-
gation kinetics, as well as hydrogen desorption pathways, during Si1
y Cy (0 0 1) gas-source molecular beam epitaxy from
Si2 H6 /CH3 SiH3 mixtures at temperatures Ts between 500 and 650 °C. Parallel D2 TPD results from C-adsorbed Si(0 0 1)
wafers exposed to varying CH3 SiH3 doses serve as reference data. Si1
y Cy (0 0 1) layer spectra consist of three peaks:
first-order b1 at 515 °C and second-order b2 at 405 °C, due to D2 desorption from Si monodeuteride and dideuteride
phases, as well as a new second-order C-induced c1 peak at 480 °C. C-adsorbed Si(0 0 1) samples with very high
CH3 SiH3 exposures yielded a higher-temperature TPD feature, corresponding to D2 desorption from surface C atoms,
which was never observed in Si1
y Cy (0 0 1) layer spectra. The Si1
y Cy (0 0 1) c1 peak arises due to desorption from Si
monodeuteride species with C backbonds. c1 occurs at a lower temperature than b1 reflecting the lower D–Si bond
strength, where Si represents surface Si atoms bonded to second-layer C atoms, as a result of charge transfer from
dangling bonds. The total integrated monohydride ðb1 þ c1 Þ intensity, and hence the dangling bond density, remains
constant with y indicating that C does not deactivate surface dangling bonds as it segregates to the second-layer during
Si1
y Cy (0 0 1) growth. Si coverages increase with y at constant Ts and with Ts at constant y. The positive Ts -dependence
shows that C segregation is kinetically limited at Ts 6 650 °C. D2 desorption activation energies from b1 , c1 and b2 sites
are 2.52, 2.22 and 1.88 eV.
Ó 2002 Elsevier Science B.V. All rights reserved.

Keywords: Thermal desorption spectroscopy; Epitaxy; Surface segregation; Silicon; Carbon; Alloys

1. Introduction and strain-state engineering of layers used in mi-

C-containing group-IV semiconductor alloys
are of intense technological and scientific interest
due to the potential they offer for both bandgap
*
Corresponding author. Tel.: +1-217-3331370; fax: +1-217-
2442278.
E-mail address: greene@mrlxp2.mrl.uiuc.edu (J.E. Greene).
croelectronic and optoelectronic devices compati-
ble with Si integrated circuit technology. Adding
C to Si1
x Gex alloy layers pseudomorphically
grown on Si(0 0 1) rapidly reduces the compressive
strain and leads to increased critical thicknesses
for nucleation of misfit dislocations. The addition
of C has also been shown to inhibit B diffusion in
npn bipolar heterojunction transistors [1], while
pseudomorphic Si1
y Cy /Si(0 0 1) structures provide

0039-6028/02/$ - see front matter Ó 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 3 9 - 6 0 2 8 ( 0 2 ) 0 1 8 2 1 - 6
476 Y.L. Foo et al. / Surface Science 513 (2002) 475–484
sufficient conduction band offset to obtain well-
defined two-dimensional electron gases for use in
modulation-doped field effect transistors (MOD-
FETs) [2].
However, the incorporation of even a few atomic
percent of C into the Si lattice is highly challenging
due to the low equilibrium solid-solubility of C in
Si, ’1017 cm
3 (Ref. [3]), and the extremely large
lattice constant mismatch between diamond (aC ¼
3:5668 A
) and Si (aSi ¼ 5:4310 A
). Complete in-
corporation of C atoms into substitutional sites in
Si1
y Cy (0 0 1) has only been achieved at C concen-
trations up to ’2 at.%, and only over a very nar-
row window of growth conditions [4].
Gas-source molecular-beam epitaxy (GS-MBE)
and ultra-high vacuum chemical vapor deposition
(UHV-CVD) have been shown to offer poten-
tial advantages over solid-source MBE. These in-
clude elimination of high-temperature evaporation
sources, higher sample throughput, better conformal
coverage, and the potential for selective epitaxy on
patterned substrates [5]. A possible disadvantage
for the growth of metastable Si1
y Cy (0 0 1) and
Si1
x
y Gex Cy (0 0 1) layers from GS-MBE/UHV-
CVD, however, is the complexity associated with
the surface chemical reactions and the dependence
of the overall film growth kinetics on the steady-
state reaction-product coverage which is in turn
dependent on deposition temperature Ts and alloy
composition.
A variety of C-containing precursors, including
C3 H8 [6], CH4 [7], CH3 SiH3 [8,9], C(SiH3 )4 and
C(SiH2 Cl)4 [10], have been used for Si1
y Cy (0 0 1)
gas-source epitaxy. Of these, monomethylsilane,
CH3 SiH3 , is of interest since it is a relatively sim-
ple molecule, is a gas at room temperature, and
contains no C–C bonds. CH3 SiH3 is believed to
dissociatively adsorb on Si(0 0 1) through nucleo-
philic substitution reactions resulting in Si–C bond
cleavage and the formation of surface CH3 and
SiH3 species which further decompose to monohy-
drides and dihydrides [11,12].
Previous reports have described the growth of
Si1
y Cy (0 0 1) layers, with y up to 0.018 and 0.03
from SiH4 /CH3 SiH3 mixtures by UHV-CVD [9]
and rapid-thermal chemical vapor deposition (RT-
CVD) [8], respectively. The UHV-CVD film growth
rate R was found to decrease with increasing y
over the entire temperature range investigated
(550 °C 6 Ts 6 650 °C) [9]. The authors proposed
that R decreases at Ts ¼ 550 °C due to surface
segregation of C to the first-layer which, in turn,
decreases the dangling bond coverage hdb (and
hence the subsequent SiH4 adsorption rate) since
the H–C bond strength is greater than that of H–
Si. However, at Ts ¼ 650 °C, where the steady-
state H coverage is near zero, R still continues to
decrease with increasing y. This was ascribed to a
different mechanism: namely a decrease in the SiH4
reactive sticking probability [9]. There are, how-
ever, no published data on C surface segregation,
steady-state C coverages hC as a function of pre-
cursor flux and Ts , or the effect of hC on H de-
sorption rates and precursor sticking probabilities
with which to test the above hypotheses.
In this article, we describe the results of experi-
ments designed to probe C incorporation and
surface segregation kinetics and their effects on
steady-state H coverages hH , and hence on film
growth kinetics, during gas-phase Si1
y Cy /Si(0 0 1)
deposition from Si2 H6 /CH3 SiH3 mixtures. We use
GS-MBE in order to take advantage of in situ
surface science probes including isotopically
tagged TPD, reflection high energy electron dif-
fraction (RHEED), low-energy electron diffraction
(LEED), and Auger electron spectroscopy (AES).
For reference, we also carry out TPD experiments
on C-adsorbed Si(0 0 1) as a function of CH3 SiH3
exposure.
D2 TPD spectra from Si1
y Cy (0 0 1) layers con-
tain, in addition to b1 and b2 peaks due to Si
monodeuteride and dideuteride surface species, a
lower-temperature C-induced monodeuteride c1
peak associated with Si surface atoms, labeled Si ,
having C backbonds. Increasing the C fraction y in
Si1
y Cy (0 0 1) layers grown at constant Ts results in
a decrease in the intensity of b1 , while the intensity
of c1 increases such that the total integrated mono-
deuteride intensity, and therefore the total dan-
gling bond density, remains constant. C segregates
strongly to the second-layer with Si coverages
hSi increasing from 0 to 0.42 ML as y is varied
from 0 to 0.026 during the growth of Si1
y Cy (0 0 1)
at Ts ¼ 600 °C. hSi also increases with Ts at con-
stant y: for example, hSi ranges from 0.1 ML at
Ts ¼ 500 °C to 0.3 ML at Ts ¼ 650 °C for
 Y.L. Foo et al. / Surface Science 513 (2002) 475–484
Si0:9952 C0:0048 (0 0 1). D2 TPD spectra from Si(0 0 1)
surfaces exposed to high CH3 SiH3 doses (2:5 
1017 –1:5  1019 cm
2 ) at Ts ¼ 650 °C exhibit, in
addition to b1 , b2 and c1 peaks, a higher-temper-
ature feature arising from the desorption of D
bonded to first-layer C atoms.
2. Experimental procedure
All Si1
y Cy (0 0 1) layers were grown in a multi-
chamber UHV GS-MBE system, described in de-
tail in Refs. [13,14]. A combination of ion and
turbomolecular pumps provide a base pressure of
’5  10
11 Torr. The growth chamber, equipped
with RHEED and a quadrupole mass spectro-
meter (QMS), is connected through a transfer
chamber to an analytical station containing pro-
visions for TPD, utilizing a heavily differentially
pumped Extrel QMS, AES, electron energy loss
spectroscopy and LEED.
Si1
y Cy /Si(0 0 1) layers, 0.10–0.45 lm thick,
were grown from Si2 H6 and CH3 SiH3 molecular
beams delivered to the substrate through individ-
ual directed tubular dosers located 3 cm from
the substrate at an angle of 45°. The dosers are
coupled to feedback-controlled constant-pressure
reservoirs in which pressures are separately moni-
tored using capacitance manometers whose signals
are in turn used to control variable leak valves.
Valve sequencing, pressures, gas flows, and film
growth temperatures are all computer controlled.
The Si(0 0 1) substrates were 1  3 cm2 plates
cleaved from 0.5-mm-thick n-type wafers (resistiv-
ity ¼ 10–20 X cm, n ¼ 2–4  1014 cm
3 ). Initial
cleaning consisted of degreasing by successive
rinses in warm trichloroethane, acetone, propanol
and deionized water. The substrates were then
subjected to four wet-chemical oxidation/etch cy-
cles comprised of the following steps: 2 min in a
2:1:1 solution of H2 O:HCl:H2 O2 , rinse in fresh
deionized water, and a 30 s etch in dilute (10%)
HF. They were blown dry with ultra-high-purity
N2 , exposed to a UV/ozone treatment which con-
sists of UV irradiation from a low-pressure Hg
lamp (15 mW cm2 ) for 30 min in air to remove C-
containing species [15], and introduced into the
deposition system through the transfer chamber.
477
There, they were degassed at 600 °C for 4 h, cooled
to 200 °C, and then rapidly heated at ’100 °C s
1
to 1100 °C for 1 min to remove the oxide. The
maximum pressure rise during oxide desorption
was 6 3  10
9 Torr for 6 10 s.
Substrates processed using the above procedure
exhibited 2  1 RHEED patterns consisting of
well-defined diffraction spots, rather than streaks,
and sharp Kikuchi lines. The layer surfaces were
thus atomically smooth with relatively large ter-
races. No C or O was detected by in situ AES.
Substrate temperatures were determined using Pt–
Rh thermocouples calibrated by optical pyrometry.
Si(0 0 1) buffer layers were grown at 800 °C
prior to commencement of Si1
y Cy (0 0 1) film
growth. The buffer layers serve two purposes. They
cover any remaining surface contamination while
simultaneously providing a more uniform dis-
tribution of terrace lengths [16]. The primary
Si1
y Cy (0 0 1) film growth temperatures were 500,
550 and 600 °C, all in the surface-reaction-limited
growth regime. The incident Si2 H6 flux was main-
tained constant at JSi2 H6 ¼ 2:2  1016 cm
2 s
1 for
all depositions while the CH3 SiH3 flux JCH3 SiH3 was
varied from 7:0  1012 to 4:2  1015 cm
2 s
1 . In a
parallel series of experiments, clean Si(0 0 1) sur-
faces were exposed to a CH3 SiH3 dose rate of
4:2  1015 cm
2 s
1 for time intervals t ¼ 1–60 min
(corresponding to doses n of 2:5  1017 –1:5  1019
cm
2 ) at 650 °C.
TPD measurements were carried out in situ on
all samples. Following Si1
y Cy (0 0 1) growth, or
CH3 SiH3 dosing of a clean Si(0 0 1) buffer layer,
the samples were quenched to <200 °C and ex-
posed to atomic deuterium until saturation cov-
erage. For this purpose, D2 was delivered through
a doser identical to those described above, but
with a hot W filament near the outlet to crack the
gas. All surface H was exchanged for D as dem-
onstrated by TPD. The TPD experiments were
performed with the sample 2 mm from the 5-mm-
diameter hole in the skimmer cone of a heavily
differentially pumped Extrel QMS. TPD spectra
were acquired using a linear heating rate of 2
°C s
1 . Deuterium was employed rather than hy-
drogen in order to suppress the background signal.
Deposited film thicknesses were measured by
microstylus profilometry while C concentrations
478 Y.L. Foo et al. / Surface Science 513 (2002) 475–484

in as-deposited layers were determined using a

Cameca IMS-5F secondary ion mass spectrometer
(SIMS) operated with a 10 keV Csþ primary ion
beam to detect 12 C. Quantification, with an exper-
imental uncertainty of 10%, was accomplished
by comparison to C ion-implanted bulk Si(0 0 1)
standards. The Si1
y Cy (0 0 1) films contained no
detectable impurities.

3. Experimental results

3.1. Si1
y Cy (0 0 1) GS-MBE

LEED patterns showed that the surfaces of all

Si1
y Cy (0 0 1) GS-MBE layers exhibit 2  1 re-
constructions with 90°-rotated domains. Fig. 1(a)
is an example, obtained in this case from a
Si0:989 C0:011 (0 0 1) layer grown at Ts ¼ 650 °C.
RHEED patterns from layers with y 6 0:0048
grown at Ts 6 550 °C consist of well-defined 2  1
diffraction spots, with nearly equi-intense funda-
mental and half-order reflections, and sharp
Kikuchi lines indicating that the film is atomically
smooth. A typical result from an Si0:9952 C0:0048 (0 0 1)
alloy is presented in Fig. 1(b). At higher C con-
centrations ðy > 0:0048Þ and/or at higher growth
temperatures (Ts > 550 °C), the RHEED patterns
become streaky. The fundamental rods broaden,
half-order to fundamental rod intensity ratios
decrease, and the amount of diffuse scattering in-
creases; all are indicative of atomic scale rough-
ening. Fig. 1(c) is a RHEED pattern from a
Si0:989 C0:011 (0 0 1) layer grown at Ts ¼ 600 °C.
Typical D2 TPD results from GS-MBE Si1
y Cy -
(0 0 1) layers are reproduced in Fig. 2. Spectra Fig. 1. (a) LEED pattern from a GS-MBE Si0:989 C0:011 layer,
’1000-A
-thick, grown on Si(0 0 1) from CH3 SiH3 /Si2 H6 at Ts ¼
from layers with y 6 0:000060 are identical to those
650 °C. RHEED patterns from GS-MBE Si1
y Cy (0 0 1) layers,
from clean Si(0 0 1). An example is shown in Fig. ’1400-A
-thick, with C fractions y grown at Ts : (b) y ¼ 0:0048,
2(a) for a y ¼ 0:000056 layer grown at Ts ¼ 600 °C. Ts ¼ 550 °C and (c) y ¼ 0:011, Ts ¼ 600 °C.
The spectra consist of two peaks, labeled b2 and
b1 , due to desorption from the 1  1 Si dideuteride
and 2  1 Si monodeuteride phases, respectively.
The peaks are centered at 405 and 515 °C. While Fig. 2(b)–(d) are D2 TPD spectra from Si1
y Cy -
b2 desorption is second-order, b1 follows first- (0 0 1) layers grown at Ts ¼ 600 °C with y ¼
order kinetics, except at very low deuterium 0:00046, 0.0048 and 0.026. As the C concentration
coverages (hD < 0:1 ML) [17], due to p-bonding- is increased at constant Ts , the TPD features
induced pairing of dangling bonds on single di- broaden (suggesting the appearance of additional
mers [18]. desorption peaks), the high-temperature feature
 Y.L. Foo et al. / Surface Science 513 (2002) 475–484 479

Fig. 2. D2 TPD spectra from GS-MBE layers Si1
y Cy (0 0 1) layers with C fractions y grown on Si(0 0 1) at Ts : (a) y ¼ 0:000056,
Ts ¼ 600 °C, (b) y ¼ 0:00046, Ts ¼ 600 °C, (c) y ¼ 0:0048, Ts ¼ 600 °C, (d) y ¼ 0:026, Ts ¼ 600 °C, (e) y ¼ 0:0048, Ts ¼ 550 °C and (f)
y ¼ 0:0048, Ts ¼ 650 °C.

n  
decreases in intensity and the intensity of the low- dhD mh Ea
¼
exp
ð1Þ
temperature feature increases. However, the total dT f kT
integrated area remains constant. Fig. 2(e), (c),
and (f), TPD spectra from Si0:9952 C0:0048 (0 0 1) al- where m is the attempt frequency, hD is the instan-
loys grown at Ts ¼ 550, 600 and 650 °C, respec- taneous D coverage, n is the order of the desorption
tively, show that the effects of increasing Ts at reaction, f is the sample heating rate, Ea is the de-
constant y are similar to those corresponding to sorption activation energy and k is Boltzmann’s
increasing y at constant Ts . constant. At high pumping speeds [20]
All TPD spectra from GS-MBE Si1
y Cy (0 0 1)  
hD ðT Þ m
layers were fit using standard Polanyi–Wigner ln ¼
IðT Þ ð2Þ
h0 f
analyses in which the desorption rate dhD =dT is
expressed as [19] for first-order desorption and
480 Y.L. Foo et al. / Surface Science 513 (2002) 475–484
h 3.2. C-adsorbed Si(0 0 1)
hD ðT Þ ¼  0
m
1þ f
h0 IðT Þ
for second-order desorption. h0 in Eqs. (2) and (3)
is the initial coverage and IðT Þ is given by
 T
Ea  e
e X
1
ð
1Þ n! 
nþ1
IðT Þ ¼  2  ð4Þ
k  e n¼1 en
1 
T0
in which e ¼ Ea =kT .
Spectra from Si1
y Cy (0 0 1) films with y 6
0:000060, including the results shown in Fig. 2(a),
were well fit with Ea and m equal to 1.88 eV and
1  1013 s
1 for b2 and 2.52 eV and 1  1015 s
1 for
b1 as previously reported for D2 TPD from clean
bulk Si(0 0 1) surfaces [21]. The agreement between
measured and calculated spectra is very good ex-
cept at high temperatures (low D coverages) where
the measured data for Si(0 0 1) and Si1
y Cy (0 0 1)
layers are higher than the calculated curves due
to the fact that b1 desorption deviates from first-
order kinetics at low hydrogen coverages where
D2 desorption becomes limited by bimolecular
recombination and is, therefore, second-order [22].
D2 TPD spectra from all Si1
y Cy (0 0 1) ðy >
0:000060Þ alloys, irrespective of y or Ts , were
equally well fit with three peaks: the initial b2 and
b1 peaks at 405 and 515 °C, together with a C-
induced c1 peak at 480 °C. Examples are shown in
Fig. 2(b)–(f). The b1 and b2 peaks have the same
physical origin, and hence the same activation
energies and frequency factors, as the equivalent
peaks in TPD spectra from clean Si(0 0 1). c1 cor-
responds to second-order D2 desorption with
Ea ¼ 2:22 eV and m ¼ 1  1014 s
1 . The integrated
intensity Ic1 of the C-induced c1 peak increases
with increasing y at constant Ts (compare Fig.
2(b)–(d)) and increasing Ts at constant y (Fig. 2(e),
(c), and (f)). This behavior is parallel to that ob-
served for the B-induced c1 peak in TPD spectra
from ultra-highly B doped Si(0 0 1):B GS-MBE
layers [23]. The c1 to b1 intensity ratio Ic1 =Ib1 in-
creases rapidly with y, ranging from ’0 with
y 6 0:000060 to 0.73 for y ¼ 0:026 at Ts ¼ 600 °C.
This suggests strong C surface segregation during
GS-MBE Si1
y Cy (0 0 1) film growth.
ð3Þ
D2 TPD spectra from C-adsorbed Si(0 0 1) sur-
faces, obtained following long exposures of clean
Si(0 0 1) buffer layers to CH3 SiH3 , are quite differ-
ent than those acquired from GS-MBE Si1
y Cy -
(0 0 1) layers. Fig. 3 shows typical spectra from
samples dosed with JCH3 SiH3 ¼ 4:2  1015 cm
2 s
1
at Ts ¼ 650 °C for t ¼ 7:5, 15, 30 and 60 min. For
short exposure times (t ¼ 1–7:5 min, correspond-
ing to doses n ¼ 2:5  1017 –1:9  1018 cm
2 ), the
TPD results exhibit a shape which is similar, with
the exception of a new extended desorption feature
at T > 515 °C, to spectra obtained from GS-MBE
Si1
y Cy (0 0 1) alloys with y > 0:00060 and com-
posed of b1 , b2 and c1 peaks. An example, corre-
sponding to t ¼ 7:5 min, is presented in Fig. 3(a).
Increasing t to 15 min (Fig. 3(b), n ¼ 3:8  1018
cm
2 ) results in an increase in the new extended
high-temperature desorption feature as b1 , b2 and
c1 decrease in intensity. Figs. 3(c) and (d) are
spectra from C-adsorbed samples dosed for t ¼ 30
and 60 min (n ¼ 7:6  1018 and 1:5  1019 cm
2 ).
The b1 , b2 and c1 peak intensities have decreased
dramatically while the high-temperature feature
has evolved into a peak, centered near 670 °C,
whose intensity increases with n. We attribute this
peak to D2 desorption from first-layer C atoms; it
occurs at higher temperatures since the D–C bond
is stronger than the D–Si bond. It is important
to note that this feature was not observed in any
of the GS-MBE Si1
y Cy (0 0 1) TPD spectra, irre-
spective of y or Ts .
4. Discussion
The in situ D2 TPD results from GS-MBE
Si1
y Cy (0 0 1) alloy layers presented in Section 3.1
exhibit, in addition to b1 Si monodeuteride and b2
dideuteride peaks at 405 and 515 °C, a new c1 peak
at 480 °C. The intensity of c1 increases with in-
creasing y at constant Ts and with increasing Ts at
constant y. A higher-temperature peak near 670
°C, due to D2 desorption from first-layer C atoms,
was obtained from Si(0 0 1) buffer layers on which
we had adsorbed C using very high CH3 SiH3 ex-
posures (n > 2:5  1017 cm
2 ) at Ts ¼ 650 °C.
 Y.L. Foo et al. / Surface Science 513 (2002) 475–484 481

Fig. 3. D2 TPD spectra from clean Si(0 0 1) surfaces exposed to a CH3 SiH3 flux JCH3 SiH3 ¼ 4:2  1015 cm
2 s
1 at Ts ¼ 650 °C for times
t: (a) 7.5 min, (b) 15 min, (c) 30 min and (d) 60 min. The open circle data points correspond to D2 TPD reference spectra from clean
Si(0 0 1) surfaces.

However, we did not observe this high-tempera-
ture peak in TPD spectra from any of our Si1
y Cy -
(0 0 1) alloy samples. Thus, we conclude that during
GS-MBE Si1
y Cy (0 0 1) film growth, adsorbed C
atoms, like B atoms in GS-MBE Si(0 0 1):B [23],
move to the second-layer primarily due to their
small size. We interpret c1 as being due to deute-
rium desorption from surface Si atoms with C
backbonds. RHEED and LEED analyses showed
that all Si1
y Cy (0 0 1) layer surfaces, irrespective of
the bulk C concentration or film growth temper-
ature, remain 2  1.
Si dimer atoms on Si(0 0 1)2  1 are in tension
and have rotated and foreshortened backbonds
associated with the reconstruction [24]. Placing C
atoms in Si dimer sites would lead to a significant
increase in the tensile strain. The small covalent
radius of C (0.77 A
compared to 1.11 A
for Si),
combined with the shorter C–Si bond length (1.89

) [25] with respect to Si–Si (2.35 A
A
) [25], results in
the second-layer being the lowest energy site for C.
This is consistent with our TPD data showing that
the activation energy for D2 desorption from C-
backbonded Si surface atoms is 0.3 eV lower than
that from Si surface atoms with Si backbonds.
This is primarily due to charge transfer, resulting
from the higher electronegativity of C, from Si
dangling bonds to the subsurface Si –C back-
bonds. Similar findings
p phave been reported for
B-adsorbed Si(111) 3  3 based on electron tun-
neling spectroscopy data [26] and for ultra-highly
B-doped Si(0 0 1)2  1 layers based upon TPD
[23].
Fig. 4 is a plot of the coverages h of the b1 and
c1 surface monohydride phases, as well as the b2
dihydride phase, obtained from the corresponding
integrated TPD peak intensities as a function of
the bulk C fraction y in Si1
y Cy (0 0 1) alloys grown
at 600 °C. hb1 decreases with y as hc1 , a direct
measure of the second-layer C coverage, increases.
However, the total integrated monohydride
coverage, hR ¼ hb1 þ hc1 , and hence the surface
dangling bond density, remains constant at 1
ML. Thus, there is no evidence for C-induced
482 Y.L. Foo et al. / Surface Science 513 (2002) 475–484
Fig. 4. b1 and c1 monodeuteride and b2 dideuteride surface
coverages h on GS-MBE Si1
y Cy (0 0 1) layers grown at Ts ¼ 600
°C as a function of y.
deactivation of surface dangling bonds. This is
quite different than for the case of ultra-highly B-
doped Si(0 0 1) GS-MBE in which charge transfer
to trivalent second-layer B atoms results in signifi-
cant dangling bond deactivation [23]. The higher
charge transfer from Si to trivalent second-layer B
atoms, compared to isoelectronic second-layer C,
is manifested in the lower B-backbonded Si mono-
deuteride desorption temperature, 470 vs 480 °C.
For clean Si(0 0 1), we obtain a hb2 =hb1 coverage
ratio of 0.23 in agreement with previous results
[24]. This is far less than the value of unity, which
would be expected for complete dideuteride cov-
erage, due to steric hindrance caused by electronic
repulsion between adsorbed H nearest neighbors
[24]. Fig. 4 shows that for Si1
y Cy (0 0 1) layers
grown at Ts ¼ 600 °C, hb2 increases slowly, as hb1
decreases, with y. Thus, the ratio hb2 =hb1 continu-
ously increases with y, ranging from 0.26 with
y ¼ 0:0010 to 0.56 with y ¼ 0:026. We attribute
this to the shorter Si –C backbond length result-
ing in wider separations between dimer rows and
hence reduced steric hindrance between neighbor-
ing monodeuteride species.
The coverage of C-backbonded Si sites on GS-
MBE Si1
y Cy (0 0 1) layers can be obtained from
our TPD data using the relation
Ic1
hSi ¼ ; ð5Þ
Ic1 þ Ib1
Fig. 5. Steady-state surface coverages hSi of C-backbonded Si
atoms during GS-MBE growth of Si0:9952 C0:0048 (0 0 1) at tem-
peratures Ts . JSi2 H6 and JCH3 SiH3 are the incident Si2 H6 and
CH3 SiH3 fluxes.
where Ic1 and Ib1 are the integrated intensities under
the c1 and b1 monodeuteride peaks respectively.
Fig. 5 shows that hSi , and hence the coverage
of second-layer C atoms, increases continuously
with Ts over the entire range investigated. For
Si0:9952 C0:0048 (0 0 1) alloys, hSi varies from 0.10 ML
at Ts ¼ 500 °C to 0.30 ML at 650 °C. This indi-
cates strong C segregation to the second-layer,
while the positive Ts -dependence shows that the
segregation is in the kinetically limited regime [27].
At higher hSi values, it is reasonable to expect
that segregated C in the second-layer will exhibit
ordering. While our LEED patterns remains 2  1,
the amount of diffuse scattering increases with in-
creasing y and Ts . This is consistent with previous
LEED results for ultra-highly B-doped Si(0 0 1)
layers [21,28] where scanning tunneling micro-
scopy (STM) studies by Wang et al. [29] showed
that B on Si(0 0 1) moves to second-layer positions
and induces local ordering with four different
polymorphs, each of which include 2  1 dimers in
the surface unit cell. Since the ordered domains are
much smaller than the LEED electron beam co-
herence length, diffraction patterns remain 2  1.
TPD spectra from CH3 SiH3 -dosed Si(0 0 1) wa-
fers reveal D2 desorption characteristics which ex-
hibit both similarities to and large differences from
those of GS-MBE Si1
y Cy (0 0 1) alloy layers grown
from Si2 H6 /CH3 SiH3 mixtures. After exposures of
 Y.L. Foo et al. / Surface Science 513 (2002) 475–484
7.5 and 15 min with JCH3 SiH3 ¼ 4:2  1015 cm
2 s
1
at Ts ¼ 650 °C, the TPD spectra (Figs. 3(a) and
(b)) exhibit a rapid decrease in b1 intensity with a
corresponding increase in c1 as the coverage of C-
backbonded Si atoms increases, consistent with
GS-MBE Si1
y Cy (0 0 1) TPD spectra in Fig. 2.
However, at these large CH3 SiH3 exposures
( P 2:8  103 ML), second-layer C coverages are
saturated and a broad higher-temperature feature,
not observed in Si1
y Cy (0 0 1) alloy spectra, emer-
ges signaling the presence of first-layer surface C.
The width of this new TPD feature arises from the
heterogeneous environment of the surface C atoms
which have both Si and C in-plane neighbors and
are also backbonded to both Si and C atoms.
Thus, the high-temperature feature corresponds to
a convolution of several TPD peaks associated
with first-layer C atoms.
With even larger CH3 SiH3 doses, the high-
temperature TPD feature increases in intensity and
narrows as first-layer C coverage increases, while
the intensities of b2 , c1 and b1 continue to decrease.
In Fig. 3(d), corresponding to the highest CH3 SiH3
exposure (n ¼ 1:5  1019 cm
2 or 2:3  104 ML),
the first-layer C peak is centered near 670 °C, well
below reported TPD results for H2 desorption
from diamond C(0 0 1)2  1 surfaces for which the
dideuteride and monodeuteride peaks occur at 900
and 970 °C, respectively [30]. This again is due to
the heterogeneous environment of both first-
and second-layer C in the present experiments.
Analogous results were demonstrated for D2 de-
sorption from Ge-adsorbed Si(0 0 1)2  1 and
Si-adsorbed Ge(0 0 1)2  1 surfaces where both
the Si b2 and b1 peak positions shift down in
temperature due to the presence of in-plane sur-
face and second-layer Ge neighbors [31].
5. Conclusions
We have carried out in situ D2 TPD experi-
ments on both C-adsorbed Si(0 0 1) and GS-MBE
Si1
y Cy (0 0 1) layers in order to probe pathways for
hydrogen desorption as well as C incorporation
and segregation kinetics during GS-MBE Si1
y Cy -
(0 0 1) deposition. D2 TPD spectra from GS-MBE
Si1
y Cy (0 0 1) layers consist of three desorption
483
peaks: b1 and b2 due to D2 desorption from Si
monodeuteride and dideuteride surface phases, as
well as a new second-order desorption peak c1 .
The b1 , b2 and c1 desorption peaks are centered at
515, 405 and 480 °C. No higher-temperature TPD
peak, corresponding to D2 desorption from sur-
face C atoms, as obtained in C-adsorbed Si(0 0 1)
spectra, was observed. The Si1
y Cy (0 0 1) c1 peak,
similar to the case for ultra-highly doped Si-
(0 0 1):B layers, arises due to D2 desorption from
C-backbonded Si monodeuteride species. c1 occurs
at a lower temperature than b1 due to the lower D–
Si bond strength as a result of charge transfer
from dangling bonds to second-layer C atoms
which have a higher electronegativity than Si. D2
desorption activation energies from b1 , c1 and b2
sites are 2.52, 2.22 and 1.88 eV.
Thus, we have demonstrated, for the first time,
that C segregates to the second-layer during GS-
MBE Si1
y Cy (0 0 1). The total integrated mono-
deuteride TPD intensity remains constant for all
Si1
y Cy (0 0 1) films indicating there is no signifi-
cant C-induced deactivation of surface dangling
bonds as was observed during ultra-highly B-
doped GS-MBE Si(0 0 1). The coverage of hSi of
C-backbonded Si , and hence the coverage of
second-layer C atoms, increases continuously with
Ts over the entire range investigated (500 °C 6 Ts 6
650 °C). For GS-MBE Si0:9952 C0:0048 (0 0 1) alloys,
hSi varies from 0.10 ML at Ts ¼ 500 °C to 0.30
ML at 650 °C. The positive Ts -dependence shows
that C segregation is in the kinetically limited
regime.
Acknowledgements
The authors acknowledge the financial sup-
port of the Materials Science Division of the
US Department of Energy (DOE) under Award
DEFG02-ER9645439. The authors also appreci-
ated the use of the Center for Microanalysis of
Materials at the University of Illinois, which is
partially supported by the DOE. PD was partially
supported by the Natural Sciences and Engineer-
ing Research Council of Canada. Y.L. Foo is
funded by the Institute of Materials Research and
Engineering (IMRE), and the Agency for Science,
484 Y.L. Foo et al. / Surface Science 513 (2002) 475–484
Technology, and Research (A*STAR) of Singa-
pore.
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