Fabrication of submicron structures in nanoparticle/polymer composite by

holographic lithography and reactive ion etching

A. Ping Zhang, Sailing He, Kyoung Tae Kim, Yong-Kyu Yoon, Ryszard Burzynski, Marek Samoc, and Paras
N. Prasad

Citation: Applied Physics Letters 93, 203509 (2008); doi: 10.1063/1.2998541

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 APPLIED PHYSICS LETTERS 93, 203509 共2008兲

Fabrication of submicron structures in nanoparticle/polymer composite

by holographic lithography and reactive ion etching
A. Ping Zhang,1 Sailing He,1 Kyoung Tae Kim,2 Yong-Kyu Yoon,2 Ryszard Burzynski,3
Marek Samoc,4,5 and Paras N. Prasad4,a兲
1
Centre for Optical and Electromagnetic Research, Department of Optical Engineering,
Zhejiang University, Hangzhou 310058, People’s Republic of China
2
Department of Electrical Engineering, State University of New York at Buffalo,
Buffalo, New York 14260, USA
3
Laser Photonics Technology, Inc., 1576 Sweet Home Rd., Amherst, New York 14228, USA
4
Institute for Lasers, Photonics and Biophotonics, State University of New York at Buffalo,
Buffalo, New York 14260, USA
5
Laser Physics Centre, Australian National University, Canberra, ACT 0200, Australia
共Received 28 May 2008; accepted 9 September 2008; published online 20 November 2008兲
We report on the fabrication of nanoparticle/polymer submicron structures by combining
holographic lithography and reactive ion etching. Silica nanoparticles are uniformly dispersed in a
共SU8兲 polymer matrix at a high concentration, and in situ polymerization 共cross-linking兲 is used
to form a nanoparticle/polymer composite. Another photosensitive SU8 layer cast upon the
nanoparticle/SU8 composite layer is structured through holographic lithography, whose pattern is
finally transferred to the nanoparticle/SU8 layer by the reactive ion etching process. Honeycomb
structures in a submicron scale are experimentally realized in the nanoparticle/SU8 composite.
© 2008 American Institute of Physics. 关DOI: 10.1063/1.2998541兴

Nanoparticles have an enabling role in various branches could be patterned over a large area by combining two-beam
of nanotechnology due to their capability of being a bridge interference lithography and the RIE process.17 In this letter,
between bulk materials and atomic or molecular structures.1,2 we apply this technology to pattern a nanoparticle/polymer
Recently, composite materials made of polymers and nano- composite in which holographic lithography 共HL兲 based on
particles have attracted great attention because of the stabi- three-beam interference process is utilized to tailor the ge-
lizing effects of the composite on the nanoparticle ometry of microstructures, and RIE is used to create the
functionalities3,4 and relative easiness and flexibility of engi- nanostructured patterns.
neering composites with advanced electrical, optical, or me- The materials chosen for this investigation are Epon SU8
chanical properties.5,6 On the other hand, submicron-scale photoresist and colloidal silica nanoparticles 共SNP兲. SU8 is
periodic structures are essential for the applications such as an excellent photoresist for laser patterning, and it has been
photonic or optoelectronic devices7,8 and biochemical utilized as a permanent structural material for micro- and
sensors.9 For instance, photons can be controlled through the nanotechnologies, e.g., microelectromechanical systems18 or
band gap of photonic crystals, which requires photonic ma- microfluidic devices,19 because of its good chemical and bio-
terials to be periodically structured on a length scale compa- chemical compatibilities.
rable to that of the wavelength of light 共i.e., the submicron Figure 1 shows the scheme of pattern formation by HL
range for the optical domain兲. Therefore, there is a need for in the top 共lithography兲 layer and its transfer by RIE to the
an efficient approach to patterning nanoparticle/polymer bottom 共nanoparticle/polymer composite兲 layer. The colloi-
composites into periodically ordered structures. Although dal SNPs are mixed with SU8 solution and spin coated on
various fabrication approaches were developed for microfab- the glass substrate. After polymerization, another photosen-
rication of polymeric devices10,11 or precise arrangement of sitive SU8 layer is casted on the top of the first layer for HL.
nanoparticles into patterns,12 the patterning of nanoparticle/ The structures created by the HL are used as a seed pattern
polymer composites necessitates special consideration due to 共or mask兲, which is then transferred to the bottom layer by
quite often great differences in mechanical and optical prop- the RIE process. Since SU8 can be effectively etched by
erties of their constituents. A practical solution is to adopt a oxygen plasma,20,21 one can simultaneously realize the pat-
two-step fabrication scheme with separated pattern definition tern transfer and “mask” removal by properly designing film
and pattern transfer procedures. Several well-developed tech- properties and process parameters. HL is employed to create
niques can be used for such a fabrication scheme. The objec- such a large-area mask. Three noncoplanar laser beams in-
tive pattern can be defined by interference lithography,13 or terfere, as shown in Fig. 1共b兲, and create a stationary spatial
nanosphere lithography,14,15 and reactive ion etching 共RIE兲15 variation in intensity, whose geometry can be tailored by
or electrodeposition,16 can perform the pattern transfer. varying polarization of the laser beams. Figures 1共c兲 and 1共d兲
Among various technologies, the fabrication based on inter- show two typical configurations of beam polarizations and
ference lithography has attracted a great deal of attention due the corresponding two-dimensional structures that are cre-
to its capability of rapidly producing large-area microstruc- ated in a negative photoresist.
tures. It was demonstrated that self-assembled nanoparticles The commercial colloidal SNPs 共Nissan Chemical,
MEK-ST兲 used in the experiments have particle sizes of
a兲
Author to whom correspondence should be addressed. Electronic mail: 10– 15 nm, and are dispersed in methyl ethyl ketone with
[email protected]. a weight ratio of 30%. They are added, together with a

0003-6951/2008/93共20兲/203509/3/$23.00
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 203509-2 Zhang et al. Appl. Phys. Lett. 93, 203509 共2008兲

FIG. 3. 共Color online兲 Etching rates of SU8 films 共black solid line兲 and
SNP/SU8 composite films 共red dash line兲 as a function of the CF4 / 共O2
+ CF4兲 flow ratio.

In order to examine the effects of embedded SNPs on the

FIG. 1. 共Color online兲 共a兲 The scheme for patterning of the nanoparticle/
process, we utilize the RIE process with O2 / CF4 etching gas
polymer composite film by HL and RIE. 共b兲 Schematics of the laser beam mixture and test the etching rates of the SU8 films containing
configuration for HL and polarization configurations for 共c兲 column struc- SNPs. With a radio frequency 共rf兲 power of 130 W and etch-
ture and 共d兲 air-hole structure. ing time of 1 min, the films are etched with different flow
rates of the O2 / CF4 gas mixture. Figure 3 shows the mea-
small amount of a photoacid generator, into the SU8/ sured etching rates for different gas flow ratios 共O2 / CF4兲,
cyclopentanone solution 共weight ratio of 10%兲, and mixed namely, 16.5 SCCM 共SCCM denotes cubic centimeter per
using ultrasonic bath to obtain the nanoparticle-dispersed minute at STP兲 /0.0 SCCM, 13.2 SCCM/ 3.3 SCCM,
photoresist solution. This solution is spin coated on a glass 9.9 SCCM/ 6.6 SCCM, 6.6 SCCM/ 9.9 SCCM, 3.3 SCCM/
substrate, and the solvent is removed by a soft bake at 95 ° C. 13.2 SCCM, and 0.0 SCCM/ 16.5 SCCM. Each data point of
After flood exposure under a UV lamp for 5 min, the film is etching rate is obtained by averaging from two experiments.
hard baked at 125 ° C to achieve polymerization 共cross- The data show that the pure SU8 film can be effectively
linking兲. Figure 2 shows the scanning electron microscopy etched by the oxygen plasma, and that the etching rate de-
共SEM兲 images of the surface of the nanoparticle/polymer creases with the increased content of CF4 in the etchant gas
film. In order to clearly show the surface of nanoparticles, a mixture. The etching rate of SU8 in pure oxygen plasma is
soft oxygen plasma process is applied before taking SEM approximately 900 nm/ min, which is about three times
images. One can see that the nanoparticles are uniformly higher than the etching rate of SU8 in pure CF4 plasma.
distributed in the SU8 matrix, and there is no significant After mixing SU8 with SNP 共SNP/ SU8 = 20 wt % 兲, how-
aggregation. The size of a polymer-coated nanoparticle is ever, the etching rate in pure oxygen plasma becomes much
around 35– 45 nm. lower 共approximately 100 nm/ min兲. It is mainly due to the
inertness of SNP to the oxygen plasma. Adding a specific
amount of CF4 can increase the etching rate. As shown in
Fig. 3, the fastest etching, at a rate of around 560 nm/ min, is
achieved when the etchant gas mixture is O2 : CF4 = 4 : 1 共vol/
vol兲.
In our experiments, visible light lithography is per-
formed by using the output beam from a cw Nd: YVO4 laser
共Coherent, Verdi V6兲 operating at 532 nm. The material
preparation and optical lithography processing are as pre-
sented before.11 Figure 4 shows an example of SU8 micro-
structures fabricated by using the configuration of laser
beams of Fig. 1共d兲. It is an air-hole structure with a triangular
symmetry having a lattice constant of 700 nm. The incident
angle for the laser beams 共angle between the beam’s k vector
and the normal to the substrate in air兲 was set to be 30° in
this fabrication.
In order to achieve simultaneous pattern transfer and
FIG. 2. SEM image showing the surface of the nanoparticle/polymer com-
mask removal, the thicknesses of the lithography layer and
posite film after a soft oxygen-plasma process. The inset shows the surface the nanoparticle/polymer layer can be optimized using the
of theisfilm
This article without the
copyrighted asoxygen-plasma process.
indicated in the data
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 203509-3 Zhang et al. Appl. Phys. Lett. 93, 203509 共2008兲

tions. The fabricated air-hole structure is of triangular sym-

metry having a lattice constant of 500 nm 共the incident angle
for the laser beams is 45°兲. One can see that the nanopar-
ticles are well ordered to form a submicron-scale honeycomb
structure. The air-hole size becomes somewhat larger than
the mask structure defined by HL due to the undercut issue.22
The pattern transfer can be further improved if the RIE sys-
tem could operate at a lower chamber pressure and tempera-
ture to improve directionality of the etching process.
The demonstrated fabrication procedure is powerful be-
cause the HL can flexibly define complex patterns and the
RIE process can be designed for different materials. Good
compatibility of HL and RIE processes is assured because
the same polymer system is used for making the composite
and the lithography films. This approach is therefore very
promising for structuring semiconductor nanocrystals or
FIG. 4. 共Color online兲 SEM image 共off-angle view兲 showing the SU8 air- quantum-dot doped polymer composites into advanced nano-
hole structure with a triangular symmetry created by HL. The inset shows photonic devices.
the top view of the same sample.
In conclusion, we have introduced a fabrication ap-
proach for patterning nanoparticle/polymer films by combin-
RIE depends on the feature size of the structure, and the ing the HL and RIE processes. A fabrication process for SNP
etching rate typically decreases when the feature size be- doped SU8 film has been established by using visible light
comes smaller. The thickness of films fabricated by spin lithography and the O2 / CF4 gas mixture RIE process. Such a
coating can be easily tailored by controlling the concentra- two-step fabrication scheme allows patterning of nanocom-
tion of polymer solution and the spinning rate. In our experi- posites with high concentration of key components such as
ments, the SU8 resin is dissolved in cyclopentanone at a nanoparticles or quantum dots. The experimental results
concentration of 10 wt %, and spin coated on a glass sub- show the powerfulness of the approach for further exploring
strate at the rate of 3500 rpm to achieve a thickness of the the utility of nanoparticle/polymer composites in photonic
nanoparticle/polymer layer of approximately 200 nm. The applications.
SU8 solution for the lithography layer, however, has a con- This work was supported in part by the US Air Force
centration of 30 wt % and is spin coated on the nanoparticle/ Office for Scientific Research and in part by National Basic
polymer layer with a speed of 2500 rpm to achieve a thick- Research Program 共973兲 of China 共No. 2004CB719800兲.
ness of the photoresist layer of approximately 800 nm. After
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