Langmuir 2000, 16, 4409-4412 4409

Nanopatterned Assembling of Colloidal Gold

Nanoparticles on Silicon
Jiwen Zheng, Zihua Zhu, Haifeng Chen, and Zhongfan Liu*
Center for Nanoscale Science & Technology (CNST) and College of Chemistry & Molecular
Engineering, Peking University, Beijing 100871, China
Received October 12, 1999. In Final Form: February 2, 2000

A quasi-one-dimensional (quasi-1D) Au nanocolloids array has been fabricated on silicon by combining

the techniques of atomic force microscopy (AFM)-based nanooxidation and chemical assembling of colloidal
nanoparticles. The silicon substrate, modified with an octadecyltrichlorosilane (OTS) monolayer, was first
subjected to a localized chemical oxidation by using conductive AFM to form silicon oxide lines. After
further modification of the oxidized region with an aminopropyltriethoxylsilane (APTES) monolayer via
selective chemical adsorption, the substrate was exposed to a colloidal suspension of gold for deposition
of gold nanoparticles. It is found that the Au nanoparticles can be selectively immobilized onto the AFM
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

tip-defined amino-terminating regions of the silicon surface, forming quasi-1D gold nanoparticle arrays.
Downloaded via INST ITALIANO DI TECNOLOGIA on October 18, 2018 at 12:41:20 (UTC).

The patterned structure is highly controllable and reproducible, which, we believe, will contribute to
studies of nanodevices and mesoscopic phenomena.

Introduction
Nanostructuring using wet colloids chemistry has
received increasing attention since the first report of
Alivisatos,1 who used a bifunctional self-assembled mono-
layer (SAM) as the molecular linker to immobilize colloidal
CdS nanoparticles onto metal surfaces to create two-
dimensional (2D) nanoparticle monolayers. Typical works
along this line were carried out by Natan,2 Liu,3 Willner,4
and Burmeister5 for the purposes of creating surface-
enhanced Raman scattering (SERS)-active substrates,
fabricating double-barrier tunneling junctions for single-
electron tunneling, preparing nanoelectrode arrays, and
nanofabrication. Great efforts have also been made on
position-controllable assembling of colloidal nanoparticles
on solid substrates.6-9 For instance, Ahmed7 reported the
combined use of electron beam lithography and the colloids
assembling technique to construct patterns of gold nano-
particles. We exploited the microcontact printing tech-
nique to create patterned assemblies of nanocolloids.8
Important progress was made by Sugimura and his
colleagues,9 who employed ultrahigh-resolution atomic
force microscopy (AFM) to locally oxidize the silicon surface
and to perform spatially selective deposition of gold
nanoparticles via specific chemical interaction. Despite
the increasing efforts in the past few years, it is still a
great challenge to develop an effective way to fabricate
well-controllable nanostructures using colloidal quantum
dots as the structural elements.
In this Letter, we demonstrate the fabrication of one-
dimensional arrays of gold nanoparticles on silicon by the
combined use of AFM-based nanooxidation and colloid
chemistry, following Sugimura’s approach. AFM was used
here to draw oxide lines by localized oxidation of silicon.
The selective immobilization of gold nanoparticles on the

* To whom correspondence should be addressed. Telephone and

Fax: +86-10-6275-7157. E-mail: lzf@chemms.chem.pku.edu.cn.
(1) Colvin, V. L.; Goldstein, A. N.; Alivisatos, A. P. J. Am. Chem. Soc.
1992, 114, 5221.
(2) Grabar, K. C.; Smith, P. C.; Musick, M. D.; Davis, J. A.; Walter,
D. G.; Jackson, M. A.; Guthrie, A. P.; Natan, M. J. J. Am. Chem. Soc.
1996, 118, 1148.
(3) Jiang, P.; Liu, Z. F. Appl. Phys. Lett. 1999, 75, 3023.
Figure 1. Experimental procedures for fabricating one-
(4) Doron, A.; Katz, E.; Willner, I. Langmuir 1995, 11, 1313. dimensional arrays of gold nanoparticles on silicon by the
(5) Burmeister, F.; Schafle, C.; Matthes, T.; Bohmisch, M.; Boneberg, combined use of AFM nanooxidation and chemical assembling
J.; Leiderer, P. Langmuir 1997, 13, 2983. techniques.

10.1021/la991332o CCC: $19.00 © 2000 American Chemical Society

Published on Web 04/21/2000
4410 Langmuir, Vol. 16, No. 10, 2000
Figure 2. 2 µm × 2 µm tapping mode AFM images of OTS-covered (a) and APTES-covered (b) silicon surfaces after soaking in
aqueous gold colloids for 12 h, showing the different affinities of CH3 and NH2 groups to gold nanoparticles.
oxide lines was achieved by the specific electrostatic
interaction of charged nanoparticles with the amine
functions of the monolayer chemisorbed on the locally
oxidized lines. By optimizing the experimental conditions
of nanooxidation and nanoparticle assembling, we have
obtained well-defined quasi-one-dimensional (quasi-1D)
arrays of gold nanoparticles on silicon.
Experimental Section
Octadecyltrichlorosilane (OTS), aminopropyltriethoxylsilane
(APTES), and HAuCl4‚3H2O were purchased from Aldrich and
used as received. An n-type Si(111) wafer with a resistivity of
0.025 Ω‚cm was used as the substrate. Ultrapure water (>17
MΩ‚cm) was used throughout the experiments. Other reagents
were of analytical grade.
The silicon substrate was pretreated following a slightly
modified RCA method:10 (1) immersion in piranha solution (H2-
SO4/H2O2 ) 7:3 v/v) at 90° for 10 min; (2) etching in a buffered
HF solution (40% HF/40% NH4F ) 1:7 v/v) for 60 s; (3) immersion
in NH3H2O/H2O2/H2O (1:1:5 v/v) at 80 °C for 10 min; (4) immersion
in HCl/H2O2/H2O (1:1:6 v/v) at 80 °C for 10 min. Finally, the
wafer was thoroughly rinsed with water and dried with high-
purity nitrogen. This pretreatment made the silicon surface rich
in hydroxyl groups, which were used to link the OTS molecules.
The OTS self-assembled monolayer (SAM) was formed on silicon
by immersing the silicon substrate in a 1 mM OTS solution of
hexadecane/tetrachlorocarbon/chloroform (10:1:1.5 v/v) for 10-
15 min,11 followed by successive rinsing in chloroform and ethanol
to remove the polymeric residuals. The monolayer surface
becomes hydrophobic, showing a water contact angle of ap-
proximately 105°.
Localized oxidation of the OTS-covered silicon substrate was
performed with a Nanoscope III atomic force microscope (Digital
Instruments, Santa Barbara, CA) in contact mode by applying
a programmed voltage pulse between a heavily doped silicon tip
and the substrate (tip negative). On the basis of an electro-
(6) Klein, D. L.; McEuen, P. L.; Katari, J. E. B.; Roth, R.; Alivisatos,
A. P. Appl. Phys. Lett. 1996, 68, 2574.
(7) Sato, T.; Ahmed, H.; Brown, D.; Johnson, B. F. G. J. Appl. Phys.
1997, 82, 696.
(8) He, H. X.; Zhang, H.; Li, Q. G.; Zhu, T.; Li, S. F. Y.; Liu, Z. F.
Langmuir, in press.
(9) Sugimura, H.; Nakagiri, N. J. Am. Chem. Soc. 1997, 119, 9226.
(10) Kern, W. RCA Rev. 1970, 31, 187.
(11) Parikh, A. N.; Allara, D. L.; Azouz, I. B.; Rondelez, F. J. Phys.
Chem. 1994, 98, 7577.
Letters
chemistry-like mechanism,12 the OTS layer underneath the AFM
tip was degraded and the underlying silicon was oxidized. The
surrounding relative humidity was approximately 58% through-
out the nanooxidation experiments. The amino-terminating
APTES monolayer was selectively formed on the lithographically
created silicon oxide regions by soaking the substrate in a 1 mM
APTES solution of ethanol for 40 min, followed by rinsing
successively in ethanol and water and blowing with high-purity
nitrogen. Finally, the sample was baked at 120 °C for 30 min to
complete the Si-O bond formation.13
The aqueous gold colloids, with an average particle size of 12
( 1 nm (confirmed by TEM), were synthesized by the method
proposed by Frens.14 The pH value of the colloidal suspensions
was about 6.1. The Au nanoparticles were assembled on the
chemically patterned silicon surface by immersing the substrate
into the Au colloids suspension for 12 h, as previously described.15
The substrate was thoroughly rinsed with ultrapure water
immediately after it was taken out of the gold suspension, and
blown dry with high-purity nitrogen. Scanning electron micros-
copy (SEM, AMRAY-1910FE) was used to characterize the
obtained nanoparticles’ pattern structures.
Results and Discussion
Figure 1 shows our basic strategy to fabricate 1D
arrays of gold nanoparticles on silicon surfaces. The
experimental procedure involves four successive steps:
(1) to coat the silicon surface with an OTS self-assembled
monolayer; (2) to draw oxide lines on the silicon by AFM
localized chemical oxidation; (3) to modify the oxidized
regions with an amino-terminating APTES self-assembled
monolayer; (4) to deposit gold nanocolloids selectively onto
the amino-terminated regions.
The specific affinity of the amino-terminating surface
to colloidal gold nanoparticles is clearly shown in Figure
2, which exhibits the tapping mode AFM images of OTS-
covered (Figure 2a) and APTES-covered (Figure 2b) silicon
surfaces after soaking in aqueous gold colloids for 12 h.
No nanoparticles were observed on the methyl-terminated
(12) Sugimura, H.; Nakagiri, N. Langmuir 1995, 11, 3623.
(13) Sato, T.; Brown, D.; Johnson, B. F. G. Chem. Commun. 1997,
1007.
(14) Frens, G. Nature Phys. Sci. 1973, 241, 20.
(15) Zhu, T.; Zhang, X.; Wang, J.; Fu, X. Y.; Liu, Z. F. Thin Solid
Films 1998, 327/329, 595.
Letters Langmuir, Vol. 16, No. 10, 2000 4411

Figure 3. 1 µm × 1 µm AFM topographic image (a) and friction force image (b) of the locally oxidized silicon surface, where the
bright lines correspond to the oxidized regions. The images were collected concurrently, and the scanning direction was from left
to right. Oxidation pulse height: 8 V. Scan rate: 4 µm/s.

silicon surface, while a monolayer of gold nanoparticles

was clearly observed on the amino-functionalized silicon
surface. The lateral size of Au nanoparticles obtained from
the AFM image falls into the range 35-40 nm, remarkably
larger than the value determined from the SEM image
(average 12 ( 1 nm). This can be attributed to the
magnification effect of the AFM tip.16 As proved in our
previous studies,17 at pH 6.1, the gold colloids are
dominantly negatively charged due to the adsorption of
anions, while the amino groups are mainly positively
charged. So the specific affinity here originates from the
strong electrostatic attractions between the negatively
charged gold nanocolloids and the positively charged
amino groups.
The localized oxidation of the OTS-covered silicon
surface was performed by applying a programmed voltage
pulse (oxidation pulse height, 8 V; scan rate, 4 µm/s)
between the conductive AFM tip and the silicon substrate.
Figure 3 shows the AFM topographic image (Figure 3a)
and friction force image (Figure 3b) of the locally oxidized
silicon surface, where the bright lines correspond to the
oxidized regions. In the topographic image, the oxidized Figure 4. AFM image of the grooves formed on OTS-covered
regions showed protrusion from other areas, while, in the silicon by localized nanooxidation and subsequent etching in
friction force image, the oxidized regions showed higher buffered HF solution. It suggests that the degradation of the
friction force, indicative of the different chemical nature. OTS layer and the formation of silicon oxide have occurred
Sugimura and his colleagues have studied the AFM-based after AFM nanooxidation.
nanooxidation of a trimethylsilyl (TMS)-modified silicon resist, leading to the dissolution of the formed silicon oxide
surface.12 They suggested that the TMS monolayer exposed into the buffered HF solution. With an optimized experi-
to a high-voltage pulse is degraded and the underlying mental condition, the line width and the interline spacing
silicon is oxidized following an electrochemical mechanism. of the AFM-derived oxide patterns on silicon could be made
This explanation is believed to hold true in the present as small as 39 and 45 nm, respectively. After localized
case. The degradation of the OTS layer and the formation nanooxidation treatment, the silicon substrate was im-
of silicon oxide have been confirmed by the etching mersed into a 1 mM APTES solution of ethanol for 40 min
experiment shown in Figure 4. When the AFM-oxidized for depositing an APTES monolayer onto the oxidized
silicon sample was immersed into a buffered HF solution regions. The evidence of APTES monolayer formation on
for 5 min, the high-voltage-exposed regions were etched the oxide lines was coming from the etching experiment.
out, forming a row of grooves. This strongly suggests that We did not find any etching effect when the APTES-treated
the degraded OTS layer cannot function as an effective sample was immersed into a buffered HF solution for 1
min, indicating that the oxidized regions have been
(16) Grabar, K. C.; Freeman, R. G.; Hommer, M. B.; Natan, M. J. J. protected by the formed APTES layer.
Anal. Chem. 1995, 67, 735.
(17) Zhu, T.; Fu, X. Y.; Mo, T.; Wang, J.; Liu, Z. F. Langmuir 1999, Figure 5 shows the SEM image of the above chemi-
15, 5197. cally patterned silicon substrate after immersion into a
4412 Langmuir, Vol. 16, No. 10, 2000
Figure 5. SEM image of the quasi-one-dimensional arrays of 12 nm gold nanoparticles formed on the chemically patterned silicon
surface. Oxidation pulse height: 8 V. Scan rate: 8 µm/s.
12 nm gold colloids suspension for 12 h, in which the
original line width and interline spacing of the amino-
terminating oxidized regions were approximately 65 and
130 nm, respectively. Obviously, deposition of gold nano-
particles was well restricted to the predefined amino
group-terminating oxidized regions, forming quasi-one-
dimensional dot arrays on the silicon surface. The adhesion
between gold nanocolloids and amino groups is electro-
static, as mentioned above. This indicates that one can
chemically position the nanoparticles on the silicon surface
in a well-controlled fashion by combining AFM nanooxi-
dation and chemical assembling techniques. As seen in
Figure 5, most of the nanoparticles are well separated
from each other, having a typical interparticle distance
of approximately 35-80 nm. Compared with the case of
gold nanoparticles assembling on a flat amino-terminating
surface (see Figure 2b), the packing disorder and coagula-
tion were more serious, possibly originating from insuf-
ficient degradation of monolayer and/or imperfect APTES
modification. We preliminarily investigated the influence
of the oxidized line width on the packing status of gold
Letters
nanoparticles and found that, with a line width < 75 nm,
the nanoparticles easily form an array on the AFM tip-
defined amino-terminating regions of a silicon surface.
In summary, we have demonstrated the combined use
of AFM nanooxidation and wet colloids chemistry for
fabricating well-controlled nanostructures with colloidal
nanoparticles being the structural elements. We have
succeeded in creating quasi-one-dimensional arrays of gold
nanoparticles on a silicon surface with an optimized
experimental condition of localized oxidation and chemical
assembling. This study may provide an experimental
approach to examining various electrical phenomena in
low-dimensional nanostructures such as single-electron
tunneling, electrical coupling between quantum dots, and
so forth. Relevant studies are in progress in this laboratory.
Acknowledgment. This work was supported by the
State Educational Committee and National Natural
Science Foundation of China.
LA991332O