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Synthesis of a fully capped mesoporous silica and its hybrids with extremely
low dielectric constant and loss
Wei Shan, Lei Chen, Yang Chu, Feipeng Zhao, Guozheng Liang , Aijuan Gu , Li Yuan
Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application, Department of Materials Science and Engineering, College of Chemistry,
Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, PR China
a r t i c l e
i n f o
Article history:
Received 24 September 2012
Received in revised form 24 January 2013
Accepted 3 April 2013
Available online 20 April 2013
Keywords:
Fully capped mesoporous silica
Polyhedral oligomeric silsesquioxane
Dielectric constant
Dielectric loss
a b s t r a c t
A novel fully capped mesoporous silica (FCMPS) was synthesized by producing a layer of linked polyhedral oligomeric silsesquioxanes (LPOSS) on the surface of a typical mesoporous silica (SBA-15). The structure of FCMPS was characterized using Fourier Transform Infrared (FTIR), Nuclear Magnetic Resonance
(29Si NMR), X-ray Diffraction (XRD), Scanning Electron Microscope (SEM), High Resolution Transmission
Electron Microscope (HRTEM), Nitrogen adsorptiondesorption and thermogravimetric (TG) analyses.
Compared with SBA-15, FCMPS has not only high surface area, pore volume and size, but also remarkably
improved thermal stability, the initial degradation temperature (Tdi) of FCMPS increases about 194 C. In
addition, FCMPS overcomes the drawback of SBA-15, exhibiting much lower and stable dielectric constant and loss. Based on the synthesis of FCMPS, the FCMPS/bismaleimide resin (BD) hybrids with different contents of FCMPS were prepared, and their dielectric properties were investigated. Results show that
FCMPS/BD hybrids have much lower and stable dielectric constant and loss than SBA-15/BD hybrids
owing to the special structure of FCMPS. With the addition of 1 wt.% FCMPS into BD resin, the dielectric
constant of the resultant hybrid is as low as about 2.50 over the whole frequency from 10 to 106 Hz;
moreover, the dielectric loss of the hybrid is almost independent on the frequency, and the dielectric loss
at higher frequencies (>103 Hz) is even lower than that of BD resin. These attractive features make FCMPS
have obvious advantage in developing materials with low dielectric constant and loss.
2013 Elsevier Inc. All rights reserved.
1. Introduction
Low dielectric constant (low-k) materials have shown great potential in microelectronic industry owing to the continuously
increasing requirements of fabricating devices with smaller size
and faster speed [14]. Nowadays, one leading approach for preparing low-k material is to introduce porous materials into a polymer by taking the advantage of the low dielectric constant (e 1)
of air in the pores [58].
Mesoporous silica (MPS) is a kind of porous material [9], however it has several tricky problems that restrict the application in
fabricating low-k polymeric hybrids. First, MPS is very easy to adsorb water (moisture) owing to the existence of rich polar and
hydrophilic silanol groups in the inner channels of MPS, as the
dielectric constant of water is as high as about 80, so MPS usually
shows a very high dielectric constant. Second, the size of the inner
channels of MPS is generally so large that the resin molecule can
enter into the channels [10]; hence the dielectric constant of the
resultant hybrids is not as low as predicted.
Corresponding authors. Tel.: +86 512 61875156; fax: +86 512 65880089.
E-mail addresses: lgzheng@suda.edu.cn (G. Liang), ajgu@suda.edu.cn (A. Gu).
1387-1811/$ - see front matter 2013 Elsevier Inc. All rights reserved.
http://dx.doi.org/10.1016/j.micromeso.2013.04.014
200
2. Experimental
2.1. Raw materials
4,40 -Bismaleimidodiphenol methane (BDM) was obtained from
Institute of Northwestern Chemical Engineering (China). 2,20 -Diallylbisphenol A (DBA) was purchased from Laiyu Chemical Factory
(China). Tetramethylammonium hydroxide pentahydrate (AR)
was purchased from Rudong Zhenfeng Yiyang Chemical Co., Ltd.,
China. SBA-15 was received from Department of Chemistry, Fudan
University, China. Toluene (AR) was purchased from Shanghai
Lingfeng Chemical Reagent Co., Ltd., China. Tetraethoxysilane
(AR), anhydrous methanol (AR), anhydrous acetone (AR) and dimethyldichlorosilane (DMDCS, AR) were all commercial products
made in China, and used as received.
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It is well known that the curing behavior of a thermosetting resin determines its crosslinked network and thus the properties of
the cured resin, so it is necessary to study the curing behavior
and the cured structure of FCMPS/BD hybrids.
Fig. 8 presents the DSC curves of BD, SBA-15/BD and FCMPS/BD
prepolymers. It can be seen that either BD, SBA-15/BD or FCMPS/
BD prepolymer has two exothermic peaks at similar temperature
ranges, indicating that SBA-15/BD and FCMPS/BD prepolymers
can be cured using the procedure as BD resin does. However, the
FCMPS/BD prepolymer has different curing mechanism from BD resin. Besides the curing reaction of BD resin, FCMPS/BD also includes the co-reaction among SiOH groups of FCMPS, and that
between SiOH groups of FCMPS and PhOH groups of DBA.
The crosslinking density (q) is another important parameter of
characterizing the cured structure for a thermosetting resin. The q
values of BD resin, SBA-15/BD and FCMPS/BD hybrids were calculated using the classical equation based on the statistical theory of
rubber elasticity as shown in Eq. (1) [41]:
q G0 =3/RT
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Fig. 5. SEM (a, c, d) and HRTEM images (b, e, and f) of SBA-15 and FCMPS.
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Table 1
Physical parameters of SBA-15 and FCMPS obtained from the N2 adsorption
desorption analyses.
Sample
SBA-15
FCMPS
444
468
6.8
8.2
0.79
0.90
where ec, e1, and e2 stand for the dielectric constant of FCMPS/BD
hybrid, BD resin and FCMPS at 104 Hz, respectively; Y1 and Y2 represent the volume fraction of BD resin and FCMPS, respectively.
The great difference between the measured and calculated
dielectric constants of FCMPS/BD hybrid is that the Mixture rule
does not consider the interaction between inorganic and organic
phases. It is known that the dielectric properties of polymers depend on the orientation and relaxation of dipoles in the applied
electric eld, the process of dipole polarization is accompanied
by the movement of polymer chain segments [43]. Therefore, the
dielectric properties are closely related to the interaction between
inorganic and organic phases. As shown in the HRTEM images of
cured SBA-15/BD and FCMPS/BD hybrids (Fig. 13), SBA-15 particles
Fig. 10. The crosslinking densities of cured BD resin, SBA-15/BD and FCMPS/BD
hybrids.
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Fig. 12. Dependence of dielectric property on frequency of cured BD resin, SBA-15/BD and FCMPS/BD hybrids.
207
4. Conclusions
An easy and new method is developed to synthesize a novel
fully capped mesoporous silica (FCMPS), of which SBA-15 is the
core, and linked POSS as a shell. FCMPS has higher porosity
(0.90 cm3/g), bigger BET surface area (468 m2/g), signicantly improved thermal stability and dielectric properties than SBA-15,
completely overcoming the disadvantages of SBA-15. Compared
with SBA-15/BD hybrids and BD resin, FCMPS/BD hybrids have
much lower and stable dielectric constant and loss owing to the
special structure of FCMPS. Especially, with the addition of 1 wt.%
FCMPS into BD resin, the dielectric constant of the resultant hybrid
is as low as about 2.50 over the whole frequency from 10 to 106 Hz.
The excellent dielectric property endows FCMPS with a great potential in developing low-k materials.
Acknowledgements
The authors thank Natural Science Foundation of China
(51173123), the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD), the Major Program of Natural Science Fundamental Research Project of Jiangsu Colleges and
Universities (11KJA430001), and Suzhou Applied Basic Research
Program (SYG201141) for nancially supporting this project.
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