Supporting information

Infrared Characterization of Interfacial Si-O Bond Formation on Silanized

Flat SiO2/Si Surfaces

Ruhai Tian,†, ‡ Oliver Seitz,§ Meng Li,¶ Wenchuang (Walter) Hu,‡ Yves Chabal,§ Jinming Gao†,*
†
Department of Chemistry, ‡Department of Electrical Engineering, §Department of Materials
Science and Engineering, University of Texas at Dallas, Richardson, Texas 75080, ¶Department of
Physics and Astronomy, Rutgers University, Piscataway, New Jersey 08854

*Corresponding author, E-mail: jinming.gao@utdallas.edu

Materials. Triethoxysilyl undecanal (TESU, >90%), triethoxysilyl butyraldehyde (TESBA, >90%),

n-octadecyltrimethoxysilane (OTMS, >90%), Carboxyethylsilanetriol, Sodium (CSS 25% in water)
were purchased from Gelest; 4A molecular sieves (1.6 mm pellets), anhydrous chlorobenzene
(>99.8%), anhydrous toluene (>99.8%), anhydrous 3-aminopropyltriethoxysilane (APTES, >98%),
trichlorosilane (TCS, >99%), and anhydrous ethanol (>99.8%) were purchased from Sigma-Aldrich
and used without further purification.

FTIR and Ellipsometry measurements. FTIR spectra were collected with a Thermo® 6700 FTIR
spectrometer in transmission mode under dry N2 purge conditions with 4 cm-1 resolution and a
DTGS detector. To detect both TO and LO phonon absorption, an incident angle of 74º was used.
Typical data acquisition involved a series of 500 scans. H-terminated silicon wafers were used as
reference to study the SiO2 spectral region (900-1300 cm-1). To distinguish the spectrum of the
silanized surface from that of the oxidized substrate, spectra taken just before the silanization
process were used as references. Ellipsometry measurements were performed with a Sentech 800
instrument. The wave-length range 330-830 nm (3.76-1.49 ev) was used in the film-thickness
measurement.

Preparation and characterization of thermal and chemical SiO2. Double sided, p-doped silicon

(100) wafers (Fz, resistivity>10 Ω·cm, Soitec USA Inc.) were first cleaned by immersing in 85℃
piranha solution (H2O2:H2SO4=1:3) for at least 20 minutes, and then SC-1 solution (1:1:5 volume
ratio of 30% H2O2, 28% NH4OH and H2O) and SC-2 solution (1:1:5 of 30% H2O2, 37% HCl and
H2O). Subsequently, the native SiO2 was removed using a 30% HF solution for 30s to obtain
hydrogen terminated silicon surfaces which were used as references for the IR spectra of SiO2. Both
thermal and chemical SiO2 were grown on hydrogen terminated silicon. Thermal oxide layers with
thicknesses of 3.4 and 4.3 nm were grown with a conventional oxidation furnace. Temperature was

controlled at 850 ℃ and the mixture gas was 10 % O2 in N2. Thermal SiO2 with 0.8-2.7 nm

thickness was obtained by etching 3.4 nm SiO2 wafer with a 0.05% HF solution for different times,
and then rinsed with DI water. The SiO2 thicknesses were determined from the integrated area of the
TO peak in the normal incidence FT-IR spectrum (referenced to hydrogen terminated silicon
surfaces), normalized to the ellipsometrically determined thickness of 21 Å as standard.1 Fresh

chemical SiO2 layers were grown in 80℃ Piranha solution for different times. The SiO2 thicknesses

were measured by ellipsometry with a refractive index of 1.465 for SiO2. All the samples were
immediately transferred into the FTIR chamber with nitrogen flowing after the surfaces were blow
dried with pure nitrogen. The LO, TO peak areas were integrated with PEAK 4.0 software and
OMNIC.

Silanization of chemical SiO2. Each SiO2 sample was cut into rectangles (2 cm×3 cm) before
surface modification. APTES and TESBA solutions used in the self-assembly process were 1% in
ethanol. Before SiO2 wafer immersion, the molecules were mixed in the solvent for 10 minutes.
After 40 min, the modified surfaces were rinsed with ethanol for 15 seconds. The self-assembly of
CSS on SiO2 surface was achieved by immersion of a SiO2 sample in a 0.5% CSS solution in water
at pH 4.0 (HCl adjusted). The modified surfaces were rinsed by DI water for 15 seconds after 40
minutes reaction. Silanization of silicon oxide surfaces with TCS was carried out in a N2 purged
glove-box. The sample was kept inside the 0.1% silane solution for ~20 hours, rinsed thoroughly
with toluene and ultrasonicated for 5 minutes in toluene. The self-assembly of TESU and OTMS
were carried out in anhydrous chlorobenzene with 1% silane for at least 1 hour. The modified
surfaces were rinsed with plenty of chlorobenzene and ethanol. The positions of initial oxide LO
peak and corresponding newly formed LO peak are listed in Table S1.
 Table S1. LO peak frequency of initial chemical SiO2 and the newly formed silane-SiO2 interface
Silane molecules APTES TESBA TESU CSS TCS OTES
SiO2 LO frequency (cm-1) 1212 1211 1219 1206 1211 1215

New LO frequency (cm-1) 1225 1219 1229 1221 1223 1222

Immobilization of polycondensed silane molecules on SiO2 surfaces. The deposition of

polycondensed TCS on SiO2 surface was carried out by fast immersion of the SiO2/Si (100) wafer
into a mixture of TCS with excess water (1/10 or 1/5 v/v). The formation of polycondensed TESU
on SiO2 surface was achieved by immersion of the SiO2/Si wafer into anhydrous chlorobenzene
containing 0.5% TESU for 48 hours. The chlorobenzene solution was kept open so that the silane
molecules could react with water molecules from the atmosphere. After the immobilization of
polycondensed silane, a white thin layer was observed with the naked eye. Figure S1 shows that a
polycondensed TESU and TCS on SiO2/Si surfaces do not have a detectable LO absorption peak in
the 1200-1260 cm-1 region. Instead, the polymerized films are characterized by two broad bands
centered at 1050 and 1125-1160 cm-1, corresponding to TO- and LO-like modes of the
polycondensed Si-O-Si bonds.

a) Poly-HSiCl3
5x10
-3 b) -1
1225 cm
Si-O-Si Poly-HSiCl3 -3
10
H-Si

-1
500 1000 1500 2000 2500 3000 1230 cm
-2
Poly-(C2H5O)3Si(CH2)10CHO 10

Si-O-Si C=O CH2

Poly-(C2H5O)3Si(CH2)10CHO

500 1000 1500 2000 2500 3000 1000 1100 1200 1300
-1 -1
Wavenumber (cm ) Wavenumber (cm )

Figure S1. Differential IR spectra of a) Poly-HSiCl3 and Poly-(C2H5O)3Si(CH2)10CHO on SiO2. b)

Comparison of Si-O absorption between the initial oxide (dash) and polycondensed silane (solid).
The SiO2 spectra are referenced to H-Si surfaces and the polycondensed silane spectra are referenced
to SiO2/Si surfaces. The LO peaks of initial SiO2/Si are marked with arrows.
Silanization of different thicknesses of thermal SiO2 by TESU. Preparation of thermal SiO2 with
different thicknesses (0.8-3.4 nm) was described previously. Before surface silanization, the
samples were rinsed sequentially with SC-1 and SC-2 solutions for 1 min, followed by a piranha
treatment for 1 min. The self-assembly of TESU was carried out in chlorobenzene with 1% TESU
for 1 hr. The modified surfaces were then rinsed with plenty of chlorobenzene and ethanol. Figure
S2 shows the LO peak positions of the initial SiO2 and TESU-silanized SiO2 as a function of the
thermal SiO2 thickness. As expected, LO peaks blue shift in the silanized samples from initial SiO2
at all thickness values. The magnitude of LO shift decreases with increasing thickness of SiO2.
More specifically, the LO frequency shifts (∆LO = LOTESU-SiO2 - LOSiO2) are 11, 10, 3 and 1 cm-1 for
SiO2 with 0.8, 0.9, 1.8 and 3.4 nm thickness, respectively. This behavior is consistent with the fact
that, to a first approximation, the magnitude of the shift is proportional to the derivative of the initial
thickness. When the LO peak position increases linearly with oxide thickness, as is the case for the
ultra-thin chemical oxides, the blue shift is constant (~12 cm-1). For the denser SiO2 films, the LO
peak position is not linear and increases less rapidly, leading to smaller and decreasing magnitude of
the blue shift.

a) 5x10
-3 b) 1260
x10
1255
LO peak position (cm )

3.4 nm
-1

1250
x10
1245
1.6 nm
1240
x10
0.9 nm 1235
x10
1230
1225
0.8 nm
1220
900 1000 1100 1200 1300 1400 0.5 1.0 1.5 2.0 2.5 3.0 3.5
-1
Wavenumber (cm ) Thickness of SiO2 (nm)

Figure S2. a) Differential IR spectra of TESU-silanized thermal SiO2 with different initial SiO2
thicknesses. The IR spectra of initial thermal SiO2 were shown as the dashed lines. Filled and open
circles represent the LO peaks in the silanized and initial SiO2, respectively. b) LO peak frequency
(cm-1) as a function of thermal SiO2 film thickness for the TESU-silanized (open squares) and initial
SiO2 (filled squares).
Kinetic analysis of TESU silanization on SiO2. The vapor deposition of TESU on SiO2 surface
was carried out in a conical flask under dry conditions. The conical flask and the homemade sample

holder were dried in an oven at 180℃ for 24 hours before use. An anhydrous chlorobenzene

solution with 0.5% silane molecule was used as a vapor source. Chlorobenzene was chosen as

solvent because its boiling point (131 ℃) is very close to the boiling point of TESU (130 ℃). The

chlorobenzene was dried with 4Å molecule sieve before use. After introduction of the silane/
chlorobenzene solution into the conical flask, the system was sealed promptly and purged with dry

nitrogen. The flask was warmed on a hotplate to keep the chlorobenzene temperature at 130 ℃ for 3

hours. After the vapor deposition process, the sample was rinsed with chlorobenzene and blow dried
with nitrogen. The sample was immersed in phosphate buffer solution (pH=7.4, 50 mM) to induce
the surface silanization and self-assembly process. The sample was then removed from the solution
at selected times (30, 90, 180, 390 min), and rinsed with chlorobenzene and ethanol before FTIR
analysis.

Reference
(1) Queeney, K.; Weldon, M.; Chang, J.; Chabal, Y.; Gurevich, A.; Sapjeta, J.; Opila, R. J. Appl.
Phys., 2000, 87, 1322-1330.