Journal of the Korean Physical Society, Vol. 37, No. 6, December 2000, pp.

878881
Improvement of Silicon Direct Bonding Using Surfaces Activated
by Hydrogen Plasma Treatment
Woo Beom Choi, Chul Min Ju, Jong Seok Lee and Man Young Sung

Department of Electrical Engineering, Korea University, Seoul 136-701

(Received 12 April 2000)
The plasma surface treatment, using hydrogen gas, of silicon wafers was studied as a pretreatment
for silicon direct bonding. Chemical reactions of the hydrogen plasma with the surfaces were used
for both surface activation and removal of surface contaminants. Exposure of the silicon wafers to
the plasma formed an active oxide layer on the surface. This layer was hydrophilic. The surface
roughness and morphology were examined as functions of the plasma exposure time and power.
The surface became smoother with shorter plasma exposure time and lower power. In addition,
the plasma surface treatment was very ecient in removing the carbon contaminants on the silicon
surface. The value of the initial surface energy, as estimated by using the crack propagation method,
was 506 mJ/m
2
, which was up to about three times higher than the value for the conventional direct
bonding method using wet chemical treatments.
I. INTRODUCTION
The silicon direct bonding process has been widely ap-
plied to silicon-on-insulator (SOI) devices, power devices,
and micromechanical sensors [13]. This bonding tech-
nology is a feasible technique for bonding silicon wafers
without the use of any adhesive material, and the bond-
ing can be attributed to intermolecular or interatomic
attractive forces between the mating surfaces [46]. For
the success of initial bonding at room temperature, the
wafer surface must be not only suciently clean, at,
and smooth, but also able to induce attractive forces by
an appropriate surface chemistry. Commercially avail-
able direct bonding methods using wet chemical cleaning
achieve surface activation by immersion in sulfuric acid
solutions or alkaline solutions [7,8]. However, these wet
chemical treatments have many disadvantages: they in-
crease the possibilities of surface roughening or chemical
contamination, must be customized for each substrate
material, and are not appropriate for multilayer materi-
als with dierent chemical reactivities [9].
This paper reports an improved method of direct wafer
bonding using surfaces activated by hydrogen plasma
treatment. The goal of this study was to investigate
the inuence of a hydrogen plasma on the bondability of
silicon surfaces and on the surface chemistry and mor-
phology. Gas-phase cleaning using a hydrogen plasma
was observed to be an especially ecient way of remov-
ing carbon contaminants on the silicon surface, and the
cleaned silicon surface was successfully activated.

E-mail: semicad@kuccnx.korea.ac.kr, Fax: +82-921-1325

II. EXPERIMENTS
Boron-doped silicon wafers with a diameters of 100
mm and a resistivities of 10 cm, which were grown us-
ing the Czochralski method, were used in this experi-
ment. In all plasma preparations below, a low-pressure
radio-frequency (RF) plasma was used. The hydrogen
plasma treatment of the silicon wafers was performed in
the reactive ion etching (RIE) mode. The base pressure
in the chamber was adjusted to 210
5
Torr before the
introduction of the plasma gas, and the pressure dur-
ing the plasma treatment was maintained at 200 mTorr.
The surface activation and the cleaning processes were
carried out in a 20-sccm hydrogen gas ow rate with a
RF power in the range of 50 to 200 W at room temper-
ature. Each pair of wafers was then taken out from the
RIE chamber, rinsed in de-ionized water for 5 min, and
spin dried just before bonding. At the next stage, two
wafers were contacted to each other at room temperature
and annealed at 900

C for 2 hours in an oxygen ambi-
ent. For a comparison of the cleaning and the bonding
eciencies, hydrophilic surfaces were formed by using
a typical wet reduction cleaning agent (RCA) solution
(H
2
O : H
2
O
2
: NH
4
OH = 5 : 1 : 1 in volume ratio) for
5 min at 80

C.
III. RESULTS AND DISCUSSION
One of the primary problems limiting applications of
direct wafer bonding is the surface roughness. Silicon
wafers, either atomically or microscopically, cannot bond
-878-
Improvement of Silicon Direct Bonding Using Surfaces Activated by Woo Beom Choi et al. -879-
Fig. 1. Eect of hydrogen plasma power and exposure
time on the rms value of the silicon surface roughness.
due to conformal limitations, if they are too rough. The
inuence of the plasma exposure time and power on the
surface roughness was examined for the silicon substrate
by using atomic force microscope (AFM). The root-
mean-square (rms) values of silicon surface roughnesses
were estimated as functions of plasma exposure time and
power, as shown in Fig. 1. The rms value of the sili-
con surface roughness was 0.12 nm before the hydrogen-
plasma treatment. The surface becomes slightly rougher
Fig. 2. Auger survey spectra from (a) the untreated silicon
wafer, (b) the silicon wafer after RCA cleaning, and (c) the
silicon wafer after hydrogen-plasma exposure.
Fig. 3. Oxide thickness measured as functions of plasma
power and exposure time.
with longer plasma exposure time and higher power. For
a constant power of 100 W, the surface roughness varies
with the plasma exposure time. When the plasma ex-
posure time exceeds a threshold value of 10 min, the
roughness increases rapidly. The reason for this increase
is known to be {111} platelet defects [10]. The highly
concentrated hydrogen ions in silicon tend to precipitate
along the {111} silicon planes, and the silicon etching re-
action occurs preferentially at positions where the {111}
platelets intersect the surface, resulting in miniature V-
grooves on the surface. As the plasma power and expo-
sure time go up, the silicon substrate temperature is in-
creased by hydrogen-ion bombardment, which enhances
the recombination of chemically active defects created in
the {111} platelet. Through the silicon etching reaction,
volatile molecules, such as SiH
x
, might be removed from
the surface.
Sucient cleanliness is essential in order to avoid inter-
face bubbles caused by surface contamination and to con-
trol the interface quality. Especially, the removal of car-
bon contaminants is a crucial problem in silicon direct-
bonding process for applications to silicon-on-insulator
(SOI)-related microelectronic devices, sensors and actu-
ators because carbon contaminants are encapsulated into
the structure by the contact with the wafer. The clean-
ing eect of the hydrogen plasma is illustrated by us-
ing Auger electron spectroscopy (AES) to compare the
chemical compositions of the samples before and after
hydrogen-plasma treatment as shown in Fig. 2. The
dominant Si, O, and C signals in the survey spectrum
obtained from the bare silicon show that the surface
mainly consists of an oxide and carbonaceous species.
The carbon signal reects an overlayer of mixed organic
molecules. The carbon signal detected on the hydrogen-
plasma-cleaned samples is signicantly weaker than the
corresponding RCA-cleaned samples. The oxide thick-
ness remaining after the dierent plasma treatments was
-880- Journal of the Korean Physical Society, Vol. 37, No. 6, December 2000
Fig. 4. Inuence of hydrogen plasma power and exposure
time on the wetting angle.
measured by AES depth proling. The oxide thickness
was taken as the depth at which the oxygen signal had
decreased to 5 % of its intensity at the surface. The
sputtering rate in the AES instrument was 1 nm/min
for SiO
2
. Figure 3 shows the oxide thickness for a set
of plasma-activated samples with an initial native oxide
thickness of 1.2 nm. The thickness of active oxide layer is
changed by varying the hydrogen-plasma exposure time
and power. The thickness is expected to be related to the
kinetic energy of the hydrogen plasma and to the reaction
with the native oxide layer. The data points show that
the resulting oxide thickness at a given exposure time
increases with the treatment power. The drawn curves
are logarithmic ts to the data. The oxide thickness ap-
pears to be close to saturation above a plasma power of
100 W. When the plasma exposure time was increased,
the same results were observed for the remaining oxide.
The surface chemistry plays a critical role in determin-
ing the surface energy of wafer direct-bonding. Surface
termination with desirable chemical groups leads to an
increase in the surface energy. In the RIE mode of the
hydrogen plasma, hydrogen radicals preferentially break
Si-O bonds at the top of the SiO
2
surface, which causes
a generation of chemically active dangling bonds at the
surface of the SiO
2
layer. This is in agreement with
the result of contact angle measurements that hydrogen-
plasma-activated samples had hydrophilic surfaces. Mea-
surement of the water-bubble contact angle showed that
the surfaces activated by hydrogen plasmas were hy-
drophilic with contact angles ranging from 5.5 to 35

,
as displayed in Fig. 4. The lowest contact angle was
obtained for hydrogen plasma with a power of 50 W and
a exposure time of 60 sec.
Figure 5(a) shows the Si-H absorption spectra of sil-
icon wafers after hydrogen-plasma treatment for 3 min
at various plasma powers obtained by Fourier transform
infrared spectroscopy (FTIR). A signicant change ap-
pears in the 2350 cm
1
band which is attributed to
Fig. 5. FTIR spectra obtained from silicon wafers after
hydrogen-plasma treatment: (a) dependence of the plasma
power at an exposure time of 3 min, and (b) dependence of
the exposure time at a plasma power of 100 W.
the stretching vibrations of the Si-H bonds in the ox-
ide. Plasma powers higher than 50 W lead to the forma-
tion of a hydrophobic layer due to the rapid absorption
of hydrogen. The absorption behavior at lower plasma
powers was similar to that at higher plasma powers if
the exposure time was lengthy, as shown in Fig. 5(b).
When the plasma power is xed at a constant power of
100 W, the absorption intensity of the 2350 cm
1
band
increases with longer plasma exposure times. The ten-
dency of these results corresponds to that obtained by
wetting angle measurements.
The high surface energy of room-temperature-bonded
wafers is desirable for making the polishing and the
cleaning of the bonded wafers easier. The high sur-
face energy also increases the probability of narrowing
the gap between wafers that are rough on a microscopic
scale. A large dierence in surface energy was observed
between hydrogen-plasma cleaning and RCA cleaning.
The initial surface energy of the specimen bonded by
hydrogen-plasma cleaning was 506 mJ/m
2
. This value
Improvement of Silicon Direct Bonding Using Surfaces Activated by Woo Beom Choi et al. -881-
is three times higher than that of the conventional RCA
cleaning method.
IV. CONCLUSIONS
The hydrogen-plasma surface treatment seems a
prospective candidate for activation of the silicon sur-
face and for removal of the carbon contaminants on the
surface at low substrate temperature. At higher plasma
powers and exposure times, the chemical oxides formed
by the hydrogen plasma treatment have Si-H bonds in
the oxides. The bonding energy at room temperature is
considerably higher (up to about three times larger) for
the hydrogen plasma treatment than for the conventional
RCA treatment.
ACKNOWLEDGMENTS
This work was nancially supported by Korea Electric
Power Corporation (KEPCO) through the Electrical En-
gineering and Science Research Institute under contract
No. 98-011. Also, it was partially funded by a special
grant from Korea University.
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