Fabrication of nanoporous polyimide of low dielectric constant

Mohd Bisyrul Hafi Othman, *Zulkifli Ahmad and Hazizan Md. Akil School of Material and Mineral Resources Engineering Universiti sains Malaysia Transkrian, 14300 Pulau Pinang *Corresponding author: zulkiflil@eng.usm.my Tel: +604-599 5259, FAX: +604-594 1011 Abstract Polyimide is a choice of material widely used in electronic packaging due to its high thermal and mechanical stability and low thermal expansion coefficient and dielectric constant. Two porous polyimides of structure shown in the following figure were successfully synthesised. The reaction scheme involve polycondensation of 3,3,4,4biphenyltetracarboxylic dianhydride with 4,4(hexafluoroisopropyllidene)-bis(4-phenoxyaniline) and 4,4-(4,4-isopropylidenediphenyl-1,1-diyldioxy)dianiline followed by thermal curing of the intermediate polyamic acid. This treatment afforded a high molecular mass polyimide of tough and thermally stable polymer. Nanofoam polyimide films were fabricated by means of sol-gel technique to give a homogeneously dispersed nano-sized voids in range 100 400 nm. Both materials showed an ultra-low dielectric constant of 2.76 and 2.84 respectively. Comparison of the treated and non-treated polyimide films showed that the gain in low dielectric constant is achieved at a considerable expanse of mechanical properties.
O N CF3 O O CF3 O CF3 N O CF3 O

dielectric constant of PIs. Recently, many works have been made to produced polyimides with lower dielectric constant, including introducing fluorinated PIs [2] and porous PI films [3]. Indiscriminate incorporation of fluorine in terms of symmetrical substitution into the polymeric chains however might yield undesireable effect [4]. Symmetric substitution of fluorine does not increase the net dipole moment of the polymer and hence, does not increase the dielectric constant. In fact, the dielectric constant decreases with symmetric fluorine substitution by a combination of lower electronic polarizability and larger free volume. Porosity in the PI structure on the other hand would introduce air into the network which would decrease the dielectric constant. This work aim to make comparison on dielectric constant and thermal property between analogous PIs with and without substituted fluorine. The PIs were fabricated in the nanofoam structure. By fabricating the foam structure with fully substituted fluorine, this work would analyse the interplay of these two parameters in optimizing the the PI dielectric property. 2. Material 4, 4-(hexaflouroisopropyllidene) diphatalic anhydride (6FDA) (97%) , 4, 4(hexaflouroisopropyllidene)-bis (4-phenoxianiline) (BDAF) (98%) and 4,4-(4,4-isopropylidenediphenyl1,1-diyldioxy)dianiline were obtained from Aldrich Chemical. N-Methyl-2-pyrrolidone (NMP, 98%) and Tetraetoxysilane (TEOS) was obtained from Across and kept dry in dessicator prior to use. 3. Experimental Procedure Preparation of polyimide films Both polymer were synthesise using similar synthetic scheme as follows: the anhydride (5 mmol, 2.5923g) was diluted with 48.10 ml of NMP solution in 100 ml 3-neck round bottom flask which were equilibrated in a water bath below 25 oC. The flask was initially purged with nitrogen gas for 5 minutes and stirred with magnetic stirring bar until the solution was homogenaous. Then the respective dianiline (5 mmol,

6FDA-BDAF
O N O O CH3 N O O CH3 O

BPDA-BAPP 1. Introduction Polyamides (PIs) are widely used as dielectric and packaging materials in microelectronic products because of their superior thermal, mechanical, dielectric and chemical resistance properties. Conventional PIs have dielectric constant ( ) in the range of 3.23.9 [1, 2]. This range of values is insufficient to fulfill the requirements of future microelectronic applications due to the trend for miniaturizing electronic devices,. Several strategies were adopted in reducing the

33rd International Electronics Manufacturing Technology Conference 2008

2.2125g) was added and the mixture was stirred vigorously maintaining at below 25 oC for 90 min under nitrogen gas flow. After the reaction was completed, the mixture was poured into 100 ml distilled water and white precipitate was formed. The beige coloured product of polyamic acid (PAA) was obtained by filtration followed by drying at 80 oC for 24 h affording a quantitative yield for both polyimides. A portion PAA solution was poured into a watch glass and cured thermally. The curing was performed by stepwise from 25 oC to 150 oC for 1 hour, 150 oC to 200 oC for 1 hour and 200 oC to 310 oC for 1 hour. Then the temperature was allowed to cool from 300 oC to 25 oC for 2 hour to give tough yellowish films. The FTIR spectrum and DSC scan for both products were recorderd. Preparation of porous polyimide A portion of intermediate polyamic acids were diluted with NMP solution (10 % v) in beaker followed by addition of tetraethoxysilane (TEOS) (SiO2 10% w /w), stirred for 6h and then the mixture was stored in closed bottle. A film were casted from the resulting mixture, immersed in hydrofluoric Acid (HF) (36.5 w/w %) to etch away silica particle for 1 hour, washed continuously with distilled water for 1h and dried in vacuum at 90 oC for 6h to remove traces of water. Determination of Dielectric constant of films. The pure and hybrid polyamic acid solution was spin-coated on silicaon wafer 1 diameter and spin at 2500 rpm for 45 second to produce uniform thin film. The thin film was dried in ambient environment and thermally cured as describe above. Then the film was cooled gradually to room temperature. The thicknesses of the film are measured by using Surfcorder 660 equipment. Aluminum layer was deposited on the upper and lower surface of the silicon wafer using evaporator equipment at pressure 3.4 x 10-5 torr. The final geometry of the coating for the test sample is shown in Fig 1.
Polyimide

to calculate the dielectric constant using the following formula.. CT K = ox o A where: C = capacitance (F) ; Tox = Film thickness (m) k = Dielectric Constant = 8.854 x 10-12 F/m A = Electrode Surface Area (m2) = (0.0005)2 = 7.854 x 10-7 m2

SEM analysis. The pure, hybrid and porous film samples were prepared and the portion of film were placed on grids Copper plate before loading on SEM chamber. The surface morphology was observed at 5 KX magnifications. The SEM equipment model used is ZESS Supra 35VP. Thermal analysis Differential Scanning Calories Analysis (DSC) was performed by using a DSC-6 analyzer (Perkin Elmer) at a heating rate 10 oCmin-1 in N2. The sample films were prepared and dried in vacuum at 90 oC overnight before measurement. The sample was heated from 28.5 oC to 300 oC, stopped at 300 oC for annealing over 1 min before the temperature reduced to 60 oC for a second scan. 3. Results and discussion A two-step solution-imidization polycondensation was employed to synthesize the polyimides as shown in Figure 2.

P-Si Aluminium

Figure 1. Geometry for C-V test This measurement was made using CV-IV measurement system Keithley Model 82 at 1 MHz current frequency. Capacitance thus obtained was used

33rd International Electronics Manufacturing Technology Conference 2008

The cured product were light brown in colours of quantitative yield. The inherent viscosities for 6FDABDAF is 1.4 dl/g while that of BPDA-BAPP is 1.1dl/g. FTIR spectra (Figures 3 and 4) for both polyimides revealed the characteristic absorptions at the region 1770 (C=O, asymmetrical stretching), 1716(C=O, symmetrical stretching), and 1370 cm1 (C-N) [5]. Peak corresponding to C-F bonds in 6FDA-BDAF are quiet difficult to establish due to overlapping with the C-C and C-O-C bonds in the 1350 1100 cm-1 region.
100.00 99.5 99.0
2964.09 2444.71 1772.32 1107.30 Sample 4

Fig 5. The SEM scan for BDAF-6FDA. (a) Pure PI (b) Hybrid PI (c) Porous PI
a b

98.5 98.0 97.5 97.0 96.5 96.0 95.5 %R 95.0 94.5

1597.69

1287.10

1717.97 1374.89

890.37

766.17

690.07 1497.58 1492.05 1169.89 1011.81 1080.50 874.68

1229.98 670.50 828.80

94.0 93.5 93.0 92.5 92.0 91.5 91.0 90.5 90.00 4000.0 3600 3200 2800 2400 2000 1800 cm-1 1600 1400 1200 1000 800 550.0
554.04 558.96 577.47 738.13 607.09 592.27

Fig 6 The SEM scan for BPDA-BAPP. (a) Pure PI Porous PI

(b)

Fig. 3 FTIR spectrum for 6FDA-BDAF

The dielectric constant for pure and porous PI is shown in theTable 1. Table 1. Dielectric constant and glass transition for the PIs. %Fluorine Tg/ oC
Pure

Hybrid

Porous

(wt)

(pure)

6FDABDAF BPDABAPP

3.05 3.41

3.25 -

2.57 2.84

24.6% 0

270 240

Fig 4. FTIR spectrum for BPDA-BAPP Porous structure of the PI films were fabricated according to the scheme as shown: First step
PAA
Sol-lprocess/ TEOS hydrolyzed Step curing

Hybrid PAA

Hybrid PI

Second step Hybrid PI

Etching HF

Porous PI

SEM image for both polyimide are shown in Fig 5 anf Fig. 6. Compared with the pure PI images, the porous structure clearly showed nano-size voids of size 80 350 nm after sol-gel and etching treatment with TEOS particles.

It can be seen that the porous structure in both polyimide shows a significant reduction in dielectric constant as compared to the pure PI. This is due to the presence of voids structure which has been fill up by air having a very low dielectric constant( = 1.0)[6]. The presence of fluorine in 6FDA-BDAF contribute further to the lowering of the dielectric constant[7]. Fluorine substitution lowers the dielectric constant by a combination of mechanisms. The incorporation of the bulky CF3 group prohibits close packing of the polymer chains and reduces interchain charge transfer of the highly polar dianhydride groups . In addition, the large fluorine atoms increase the free volume fraction in the polymer essentially reducing the number of polarizable groups in a unit volume. Fluorine substitution also lowers the electronic polarization in the polymer due to the large electronegativity of the C F bond [8]. In the case of 6FDA-BDAF, the hybrid structure showed the highest dielectric constant. This is as expected due to the present of inorganic silica particles with a high dielectric constant( = 3.9). The Tg for 6FDA-BDAF is higher than BPDA-BAPP. This

33rd International Electronics Manufacturing Technology Conference 2008

might be due to the chain flexibility of the latter in particular the flexible single bond joining the biphenyl ring in the anhydride moiety as compared to the rigid hexafluoroisopropylidene bridge of the analogous anhydride of the former. The presence of bulky fluorinated methyl group in 6FDA-BDAF induce chain rigidity which further reduce the Tg value compared to BDPA-BAPP. Acknowledgement The main author wish to thank MOSTI/USM for FRGS grant No:6071003 awarded to undertake this project. References 1. Chun-Kuo Min, Tai-Bor Wu, Wei-Ta Yang, and ChiLun Chen. 2008. Composites Science and Technology. 68 15701578. 2. Vora RH, Gopala Krishnan PS, Goh SH, Chung TS. 2001. Adv Funct Mater. , 11(5) 362373. 3. Cha HJ, Hedrick J, DiPietro RA, Blume T, Beyers R, Yoon DY. 1996. Applied Phys Lett. 68(14) 1930 1932. 4. G. Hougman, G.Tesoro, A. Viehbeck, 1996, Macromolecules, 29, 3453 5. Hongshen Li, Jingang Liu, Kai Wang, Lin Fan and Shiyong Yang, 2006, Polymer 47, Issue 4 , 1443-1450 6. Maxwell-Garnet, J.C. Philos. Trans. R Soc , 1982, 15:2033 7. Haidar M, Chenevey E., Vora R.H., Cooper W., Glick A, Jaffe M.,1991, Mater. Res. Soc Symp Proc,

227:35 8. J.L. Hedrick et al. Reactive & Functional Polymers 1996, 30, 43-53); A.K. St.Clair, T.L. St.Clair, W.P. Winfree, ACS Polym. Matls.: Sci. and Eng., 1988, 59 28; Simpson J.O., StClair A.K., Thin Solid Films,1997, 308 309, 480 - 485

33rd International Electronics Manufacturing Technology Conference 2008