EPITAXIAL SILICON GROWTH IN A REDUCED

PRESSURE AND TEMPERATURE CVD REACTOR

J. Regolini, D. Bensahel, J. Mercier, E. Scheid

To cite this version:

J. Regolini, D. Bensahel, J. Mercier, E. Scheid. EPITAXIAL SILICON GROWTH IN A REDUCED
PRESSURE AND TEMPERATURE CVD REACTOR. Journal de Physique Colloques, 1989, 50 (C5),
pp.C5-519-C5-527. �10.1051/jphyscol:1989561�. �jpa-00229592�

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 JOURNAL DE PHYSIQUE
C o l l o q u e C5, s u p p l 6 m e n t au n"5, T o m e 5 0 , m a i 1 9 8 9

EPITAXIAL SILICON GROWTH IN A REDUCED PRESSURE AND TEMPERATURE CVD REACTOR

J.L. REGOLINI, D. BENSAHEL, J. MERCIER* a n d E. SCHEID'"

C e n t r e N a t i o n a l d ' E t u d e s des T 6 1 6 c o m r n u n i c a t i o n s , B P . 98, F - 3 8 2 4 3 M e y l a n
Fedex, F r a n c e
L E P E S / C N R S , avenue d e s M a r t y r s , F - 3 8 0 4 2 G r e n o b l e C e d e x , F r a n c e
* " L P C S / C N R S , avenue d e s M a r t y r s , F - 3 8 0 3 1 G r e n o b l e C e d e x , F r a n c e

RESUME

En procede thermique rapide dans un systeme sous pression totale de

quelques torrs, I'epitaxie selective du silicium est realisee B des temperatures aussi
basses que 650°C. Les sources gazeuses du silicium sont soit le silane soit le
dichlorosilane (DCS) diluees dans I'hydrogene etlou I'helium.
Les aspects cinetiques de la croissnce du siljcjum dans Ies deux systemes
DCS/H2 et SiH4/HCI/H2 sont presentes et discutes. Le taux de croissance avec DCS est
fonction lineaire de la pression partielle d'hydrogene alors que pour SiH4/HCI, une
variation quadratique traduit les resultats experimentaux.
La selectivite ainsi obtenue est expliquee selon un modele de
decomposition des gaz reactifs et n'est pas affectee par la nature du gaz porteur,
alors que le taux de croissance I'est. Nos resultats montrent I'existence de conditions
experimentales pour lesquelles le taux de croissance est presque independant de la
temperature.
Ce type de CVD, a pression et temperature reduites, apporte une
contribution positive aux problemes poses par la VLSl qu'exige des jonctions abruptes
des couches epitaxiques selectives et un procede basse temperature.

ABSTRACT

In a Rapid Thermal Processing system working at a total pressure of a

few torr we have obtained Selective Epitaxial Growth of Si at temperatures as low as
650°C. The studied gas systems are based on the decomposition of either silane or
dichlorosilane (DCS) diluted in hydrogen and/or helium.
The kinetic aspects of the two systems: DCS/Hzand SiH4/HCI/H2 are
presented and discussed. The growth rate for DCS is found to be a linear function of

Article published online by EDP Sciences and available at http://dx.doi.org/10.1051/jphyscol:1989561

C5-520 JOURNAL DE PHYSIQUE

the hydrogen partial pressure. Nevertheless, for SiHdHCI a quadratic approach fits
the experimental results better.
The obtained selectivity is explained b y the reacting gases decomposition
model and is not affected by the nature of the carrier gas as the growth rate is. These
results show the existence of experimental conditions under which the growth rate is
nearly temperature independent.
A new contribution to the VLSI challenge is provided by this type o f CVD
at reduced pressure and temperature for which abrupt junctions, selective epitaxial
layers and low temperature processes are required.

INTRODUCTION

Selective silicon epitaxy is a promising technique for very large scale

integration (VLSI) where device isolation is in the range of the submicron scale
geometry. In addition abrupt transitions in dopant concentration cannot be achieved
using conventional high temperature (>lOOO°C) CVD. As a result a reduction in the
epitaxial temperature has a significant effect on high performance integrated
circuits as shown for an isolated npn bipolar transistor by Srinivasan and Meyerson
i l l . The n+ buried layer profile is very sensitive to the epitaxial deposition
temperature. Moreover, recent results have shown the good performance of a Si/Si-Ge
heterojunction bipolar transistor made by low temperature CVD 121. In this case, the
thermal exposure should be minimized since these layers are metastable. Thus,
excessive thermal exposure will cause the films to relax and form misfit
dislocations which may degrade the device performance.
A considerable amount of research has been done on low temperature
epitaxy. Meyerson et al. I31 have demonstrated that device quality material can be
obtained by CVD at temperatures as low as 750°C in an ultrahigh vacuum
environment. A plasma assisted system is also used by Donahue and Reif /4/
achieving good quality material, and Vescan et al. 151 using a ultrahigh vacuum
reactor down to 760°C. Device quality epitaxial layers can be grown in a
commercially available reactor by Borland and Drowley 161 in a pressure range of 10
to 100 torr and at a temperature of about 850°C.
We previouly presented /7,8/ a selective epitaxial growth study of silicon
on patterned wafers, in which we showed the full selectivity obtained using DCS in
H2 without any HCI addition. We also compared the DCSlH2 system with the SiH4/H2
and the SiH4/HCI/H2 systems and concluded that selectivity is also a strong
function of the total pressure of the system. No addition of HCI is needed when using
DCS in H2 in the pressure range investigated in our study.
The aim of the present paper is to show how selectivity does not depend
on the nature of the carrier gas while the growth rate does. In addition the growth
rate behaviour, when H2 or He are used as a carrier gas, will be studied for the three
systems: DCS, SiH4 and SiH4lHCI.
EXPERIMENTAL

Our experimental set-up consists of a rapid thermal CVD system using a

bank of tungsten lamps as a source of radiant heat. The system was pioneered by J. F.
Gibbons 191 and the process was named: "Limited Reaction Processing". The actual
reactor is a horizontal cold-wall air cooled silica chamber where the base pressure
is about 2 mtorr obtained simply by a mechanical oil pump with a molecular sieve oil
trap. The substrate temperature, rather than the gas flow, is used as a switch to turn
the CVD reaction on and off. The substrate surface is only hot while the reaction is
occurring. The sample temperature rises at about 200°C/sec and cools down to about
200°C in 20 sec.
After loading the sample the system is purged using H2 which is also
generally used as a carrier gas. Before deposition, the sample is subjected to an "in
situ" cleaning step which depends on the sample surface history. For example, the "as
received" wafers should be cleaned using a high temperature cycle of a few seconds
(lOOO°C, 30 sec) under H21HCI to etch the native oxide from the silicon surface. If
only low temperature cycles are allowed, a chemical pre-clean procedure before
loading is imperative. In this case, an RCA chemical cleaning / l o / will precede a low
temperature "in situ" process (800°C, 1 min), which can include deep UV radiation
I 1 11.
In general, all the studied layers were specular and shiny. Some remaining
defects could be found since no special care was taken with the laboratory
environment and/or sample handling. Patterned in SOn, (100) 4" wafers were used in
this study. The growth rate (G) of the epi-layers were measured by a profilometer and
the wafer temperature was measured by a thin thermocouple attached to a test wafer
under the same experimental conditions. Reactive and carrier gases were all
electronic grade and no special purification was used, their flow being established by
flowmeters prior to the temperature cycle. The reactive and carrier gas partial
pressures indicated in different plots were all measured using a pressure induced
capacitance manometer. As our system works under a reduced dynamic pressure, the
partial pressure of each gas also depends on the pumping system impedance as well
as on the total pressure and flow ratios. Thus, when the partial pressure of a gas is
used as a variable, this variable represents the measured value rather than the
calculated one as is possible in a static system. The extreme simplicity of the
reactor, its negligeable thermal and chemical inertness, together with the easy
control of gas pressure and rapid thermal cycle, should be noted. The versatility of
the system has been demonstrated by growing low' temperature silicon dioxide on
compound semiconductors like InP 1121 and the selective deposition of silicides
without silicon consumption 1131.
 JOURNAL DE PHYSIQUE

RESULTS AND DISCUSSION

I ) . - Influence on G of deposition temperature

Using H2 as a carrier gas at 2 slm with a constant total pressure of 2

torr, we obtained the growth rate G as a function of temperature, for a given reacting
gas flow rate as shown in Figure 1 in an Arrhenius type plot.

7 8 9 1 0 11
lo4 / TI°K]
Figure 1.- The growth rate of silane and DCS in an Arrhenius plot

Two regions can be easily distinguished:

- a high T region (T>850°C) where the crystal growth is limited by the
supply of reactant via the gas phase diffusion and
- a low T region (Tc850°C) where the G values are controlled by the
sample surface reactions which are activated.
For silane we measured an apparent activation energy Ea of 38 kcallmol (below
750°C), curve (a), which is close to the dissociation energy of the silylene molecule:

and compares quite well with the values obtained from the literature 114,151.
On the other hand, the measured Ea value for the DCS decomposition is
about 59 kcallmol which is slightly higher than previously published values (between
40 and 50 kcallmol 116,171). If a certain reaction is rate-limiting, our result
implies that this reaction is different from the one generally assumed:

In the high temperature region, however, no doubt exists in assuming a

gas diffusion limitation. Indeed, the G values are very weakly temperature dependent
i.e. in proportion to the molecular diffusion coefficients ( To.9 ) 171. In addition, the G
values for silane and DCS are almost equal. This is simply because the diffusion
coefficients of both gases are in the reciprocal ratio of the flow rates (40 and 80
sccm respectively).

2).- Influence on G of the reactive aas injection

The growth rate for both systems exhibits a reaction order A defined by
the equation:

where p~ stands for the partial pressure of SiH4 or DCS, K is a constant at a given T,
and A is close to one at 900°C. At 800°C and below, this A value is well below one
which is a clue to a Langmuir-Hinshelwood type adsorption mechanism 1181. For the
SiH4 case, we have already mentioned that the SiH2 reaction at the surface must be
involved. For the DCS case it seems that SiCI2 should not be involved due to Ea.

3).- Influence on G of the hvdroaen partial pressure

In order to maintain the total pressure constant, we used H2 and He as a

mixed carrier gas. In Figure 2 we compare the two systems, SiH4IH2 and DCSIH2, by
plotting the G values as a function of the H2 partial pressure. The DCS curve at 750°C
is fairly constant.

Figure 2.- The growth rate of silane and DCS as a function of hydrogen partial
pressure for two different temperatures.
 JOURNAL DE PHYSIQUE

At 900°C the DCS shows an increase in G when increasing the H2 partial

pressure pH2. Just the opposite is measured for the SiH4 system where a slight
decrease is only observed at these two temperatures. This general behaviour can be
explained as follows: for DCS, at high T, the increase in growth rate with increasing
pH2 should be attributed to the reactive gas diffusion coefficient which is higher in
H 2 than in He (0.39 cm21s and 0.35 cm21s respectively as calculated according to
1191). At low T this growth rate is fairly constant which correlates perfectly with
the proposed DCS decomposition, where no H2 is involvedl81. In the case of SiH4, at
high and low T, there is a growth rate decrease when increasing pH2 because the
silylene decomposition produces hydrogen, (according to [I]). Thus, the presence of H2
as a carrier gas will depress this reaction giving lower G values.
To explain all the DCS results in the activated regime we propose a
surface-reaction scheme based on:

SiH2CI2 -> SiHCl + HCI [41

for which lshitani et al. 1201 have given the dissociation energy of 61 kcallmol,
close to our value of 59 kcallmol. Also P. Ho et al. 1211 mentioned the existence of
SiHCl as a product at atmospheric and reduced total pressures. This scheme does not
involve H2, thus qualitatively fitting our observations. As HCI is also a product , it
explains a very interesting feature of our process, namely selective epitaxy.
Selective epitaxial growth is obtained throughout the whole studied
temperature range (1100°C - 650°C) when using DCS diluted in Hp and no epi-layer
thickness limitation has been observed. The selectivity can be easily explained by the
silicon nuclei reduction on the SiO2 mask through the HCI by product. Increasing the
HCI concentration will produce a rapid linear decrease in growth rate These
results eleiminate any explanations based on: SiCI2 + H2 -> Si + 2HCI
1000 900 800 700 ["C]
lo4

74 kcallmol
.- Selectiv.
E without
Y
HCI
Selectiv.
with
2 sccm HCI

10'
7 8 9 10 11
10 / T [OK]
Figure 3.- Growth rate as a function of the reciprocal temperature for the
SiH4/HCI/H2 system showing the region where selectivity is obtained only with SiH4.
 When using silane, as reacting gas, selectivity is also obtained at temperatures
above 950°C, and the addition of HCI is not needed, as shown in Figure 3
On the other hand, below that temperature, just a few percent of the SiH4
concentration of HCI is needed to obtain full selectivity. In this case 2 sccm of HCI
in 20 sccrn of SiH4 diluted in 2 slm of H2. Accordingly the activation energy Ea is
affected: from 38 kcal/mol for the SiH4/H2 system it goes to 74 kcal/mol for the
SiH4/HCI/H2 system and selectivity is obtained up to 650°C.
In order to study the chemical reactions in the SiH4/HCI/H2/He system,
the growth rate variation was measured as a function of pH2 and G was plotted
versus the square of this pressure as shown in Figure 4.

0 1 2 3 4
(pH2 [torr])

Figure 4.- The growth rate for the two systems DCS and SiH4/HCI diluted in a gas
mixture of H2 and He are plotted as a function of the H2 partial pressure.

If we propose a chemical reaction similar to that proposed for the DCS/H2

system, the following equations hold:

SiH4 + HCI -> SiHCl + 2H2 [51

SiHCI + -> (SiHCI)* [GI

which means that the growth rate should depend on the second power of the hydrogen
partial pressure and the limiting reaction will come from:

(SiHCI)* -> Si* + HCI [71

where "*" means adsorbed species or a vacant site. Curve (a) from Fig. 4 shows this
quadratic behaviour for H2 pressures above 1 torr. Curve (b) is the same qualitative
C5-526 JOURNAL DE PHYSIQUE

result already shown in Fig. 2 where G is fairly constant above 1 torr of Hp. Curve (c)
corresponds to the same system as (a) at 900°C, which follows a similar beh-aviour to
DCS at 900°C shown in Fig. 2.
What is striking in the present picture is the important decrease in
growth rate at low hydrogen partial pressure, i.e., when there is more He than H2 as a
carrier gas (the total pressure being constant) and in the presence of HCI. This
behaviour is nearly temperature independent. Curve (a), at 750°C, is in the activated
regime and curve (c), at 900°C, in the diffusional one. In all cases the G values
decrease dramatically under 100% He as a carrier gas, whatever the system, i.e.,
DCSIHe or SiH4lHCIlHe. The growth rate'is more affected at 900°C than at 750°C and
full selectivity is preserved in the two systems. To our knowledge the growth rate,
under 100% He as a carrier gas, is lower than under 100% Hp because of a depletion of
reactant in the gas phase. The presence of He enhances the homogeneous
decomposition of reacting gases and the products are carried away from the reactor.
A clear advantage of this system, SiH4/HCI/H2/He, is in the region where
the volumetric ratio for HpIHe is about one: the G values are almost the same for 750
and for 900°C (around 600 Atmin which is fairly high). This implies that the addition
of He is able to remove the pathological sensitivity towards T of the growth rate in
the SiH4IHCIlHp system.

CONCLUSION

Full selectivity has been obtained with only DCS diluted in Hp. However, in
the silane system, a small percentage of HCI in silane is sufficient to obtain
selectivity up to 650°C. This is the main characteristic of our system working in the
torr pressure regime. The etching of silicon by the presence of HCI is enhanced by
this reduced pressure regime.
The rapid thermal process applied to Si epitaxial growth has proven its
capability of growing selectively good epitaxial layers with a high degree of control
and under a wide spectrum of experimental conditions.
The fact that growth rates can be controllably varied from 10 to 1000
Almin makes this procedure a very good candidate for V and ULSl applications.

ACKNOWLEDGEMENTS

The authors would like to thank Mrs. M. Timmins for reading of the
manuscript and R. Carre for technical assistance.

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