Micro- and Nanoporous Materials Developed ... - ACS Publications

Chapter 17 M i c r o - and Nanoporous Materials Developed Using

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Supercritical

CO

2

Novel Synthetic Methods for the Development of Micro- and Nanoporous Materials Toward Microelectronic Applications 1

Sara N. Paisner and Joseph M . DeSimone

1,2

1

Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, NC 27599 Department of Chemical Engineering, North Carolina State University, Raleigh, NC 27606

2

A number of different types of nanoporous materials for use in low dielectric constant applications have been developed in recent years, including nanoporous silica, polyimides, poly(arylethers), and poly(methyl silsesquioxanes). Recently, much research has been done in the field of supercritical carbon dioxide (scCO ) and its use in the synthesis of polymers for microelectronic applications. A variety of different methods using supercritical C 0 to form micro- and nanoporous materials towards applications in the microelectronic industry are described. 2

2

© 2004 American Chemical Society

Lin et al.; Polymers for Microelectronics and Nanoelectronics ACS Symposium Series; American Chemical Society: Washington, DC, 2004.

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224

Introduction

Demand for low dielectric constant (k) materials in the microelectronics industry has led to extensive efforts to explore the applicability of porous materials, especially nanoporous materials. Nanoporous or mesoporous materials have potential utility in many applications including membranes, sensors, waveguides, dielectrics, and microfluidic channels. * For these uses, a number of different types of nanoporous materials for microelectronic application have been developed. They include nanoporous silica, " polyimides, poly(arylethers), " and poly(methyl silsesquioxanes). " Most of these ultralow-fc materials are prepared by introducing air-filled pores into the film, taking advantage of air's low dielectric constant ( £ i r = 1). For microelectronic applications, control over the pore size, shape and distribution is critical to obtain materials with suitable mechanical and electrical properties. Recently, a large amount of research has been done to develop chemistry in scC0 . The potential benefits of using C 0 to make nanoporous materials are numerous, and in recent years many C 0 based processes have proven their worth in other industries, such as industrial extraction processes, polymer processing, and even consumer C0 -based garment cleaning. The low viscosity and surface tension of C 0 potentially allow it to address certain problems associated with microelectronics industry in general, and the synthesis of micro- and nanoporous materials in particular. Another important advantage of using C 0 as a solvent in material synthesis is that it is relatively environmentally benign. Unlike organic solvents and aqueous solutions used in conventional micro- and nanoporous material synthesis, C 0 is non-toxic and readily recyclable. In an industry where an enormous amount of organic and aqueous waste is produced daily, the introduction of a readily recyclable, environmentally benign solvent has the potential to dramatically reduce the cost, bothfinanciallyand environmentally, of microchip fabrication. This review chapter will focus primarily on the synthesis of nanoporous materials using C 0 in one of two main methods. The first is via extraction, which takes advantage of the differing solubilities of polymers in scCG . The second method involves foaming of materials with C0 as the blowing agent. Both methods have resulted in micro- and nanoporous polymers some of which may have potential applications as low dielectric constant materials. 1

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Formation of Porous Materials via scC0 Extraction 2

By taking advantage of the differing solubilities of polymers in scC0 , novel nano- and microporous materials can been developed. In particular block and 2


225 graft copolymers can form micro-phase separated morphologies such as spheres, cylinders and lamellae, which can be used to control the orientation of nanostructures of large areas. The molecular structure and M of the second block segment determines the pore size and volume fraction of the dispersed phase. Selective removal of the minority component from the crosslinked material then leaves a matrix filled with nanoscopic voids. Block copolymers which contain a thermally labile segment have been used to form nanoporous materials. Following this approach, we have focused on the formation of phase separated polystyrene-g-poly(dimethylsiloxane) (PS-gPDMS) and PS-è-PDMS copolymers (Figure 1) followed by chemical decomposition of the PDMS blocks using acid in scC0 . Once the PDMS decomposed, it was extracted out from the PS matrix using scC0 , in which the oligomeric siloxanes were highly soluble. This resulted in nanoporous materials, as the size of the PDMS spheres within the PS matrix could be controlled by controlling the weight % of the PDMS block. TEM analysis of a film formed by evaporation from chloroform, showed 5-8 nm size spheres of PDMS in a PS matrix (Figure 2). Thin films were formed by spin coating on to a silicon wafer from trifluorotoluene and SEM analysis of the thin films show a film thickness of approximately 500 to 700 nm. By DSC, two T 's are observed; 86 °C for PS, 106 °C for PDMS as well as a T at -46 °C for PDMS. The PDMS grafts (or blocks) of these materials were decomposed into oligomers by trifluoroacetic acid in scC0 . By SEM analysis of cross sections of films, the sizes of the pores were determined to be approximately 5-20 nm (Figure 3). A second example of scC0 as an a development solvent for use in the formation of low-£ materials was demonstrated using hot-filament chemical vapor deposition (HFCVD, also known as pyrolytic CVD) to form directly patterned low-* films. HFCVD using hexafluoropropylene oxide (HFPO) as the precursor gas has been shown to produce fluorocarbon films spectroscopically similar to polytetrafluoroethylene (PTFE, k = 2.0), a material with a very low dielectric constant. Films formed from this process were exposed to e-beam doses followed by scC0 development to determine contrast curves. The contrast for each sample described correlated qualitatively with the concentration of OH and C=0 species, and the lower the OH/CF ratio, the higher the contrast under e-beam exposure. Both of these sets of values can be controlled by careful design of the HFCVD process which was described previously. By developing low-& materials compatible with the damascene process in scC0 , multiple steps presently required to produce patterned insulators can potentially be removed. A method which involves the use of scC0 to extract out oligomers from a polymer matrix has also been described. Plasma enhanced chemical vapor deposition (PECVD) was used to obtain siloxane films from tetravinyltetramethylcyclotetrasiloxane, (TVTMCTS, a liquid source) mixed in 28

w

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0+

PS-g-PDMS

PS-6-PDMS

"^^ H

^^ 1

—Bu

Figure L Synthesis ofPS-b-PDMSandPS-g-PDMS

AIBN 75 °C, Cyclohexane

linkage

unstable C-O-Si


~1g

-Mr

m

η _85


227

Figure 2. TEM at high magnification ofPDMS spheres in a PS matrix.

Figure 5. SEM ofcross section ofPS nanoporousfilmafter PDMS removal in s c C Û 2 using trifluoroacetic acid.


228 with a C F gas and H plasma. This mixture was deposited on silicon substrates using PECVD to obtain composite films which were stable to 400 °C. The films were then pressurized with scC0 at 200 °C and 8650 psi for 8h to extract out the low molecular oligomers. This was possible as low molecular weight oligomers of this siloxane were soluble in seC0 , whereas the high molecular weight materials were not. Once the oligomers were removed, a porous film was obtained. Dielectric constants of k = 2.5 to 3.3 were observed in the materials extracted with scC0 . 2

8

2

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Carbon Dioxide Foaming Another approach for forming micro- and nanoporous materials is via scC0 foaming. Use of environmentally friendly physical blowing agents in their supercritical or non-supercritical state has become important in the past few decades. For use of foamed materials in any microelectronic features, pore size must be much smaller than the film thickness, as otherwise the foams may collapse. One physical foaming process involving glassy poly(ether imide)s and poly(ether sulfone)s using C 0 has been investigated. Two types of porosities were observed, closed microcellular and bicontinuous. In this work, the foaming behaviors of thin (~75μΜ) extruded poly(ether imide) (PEI) and poly(ether sulfone) (PES) films were studied (Table I). Porous materials were formed using a discontinuous solid-state microcellular foaming process with C 0 as the blowing agent. Temperatureconcentration conditions ("foam diagrams") that mark the foaming region (i.e. where the C0 -saturated polymer/gas mixture changes into a cellular structure) were determined. Closed-cellular morphologies were no longer observed above certain C 0 pressures in the mixture and instead, nanoporous bicontinuous foams were observed. For example, closed cell pores were seen until ca. 40 and 50 bar for PEI and PES, respectively, after which the structure became bicontinuous. A good guide for the foaming boundaries were determined to be the T of the polymer/gas mixture and what the authors called the "upper foaming temperature limit." This temperature was where cells became unstable due to C 0 loss (due to diffusion) and a strong decrease in viscosity of die polymer was observed (Figure 4). Interestingly, increasing C 0 saturations levels to ca. 47 cm was found to cause cell diameters to suddenly decrease below 100 nm and cell densities to increase by two orders of magnitude, up to 10 cells/cm (Figure 5). This was accompanied by, and thought to be due to, the change from a closed pore to bicontinuous morphology.

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Figure 4. Mass density ofPEI as a function of the dissolved amount of CO2 and the foaming temperature. Numbers written close to the straight lines represent the mass density ofthe foam in g/cm . The mass density contours are constructed by linear interpolationfromexperimental data series of nine different saturation pressures, equally distributed over the investigated concentration range. The glass transition temperature (Tg) and T are presented dependant on the dissolved amount of CO* The straight line represents a least-squaresfitofthe experimental glass transition data. (Reprintedfromreference 36. Copyright 2001 American Chemical Society.) 3

upper



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Figure 5. Cell densities ofporous PES morphologies vs. the CO2 concentration of the saturated polymers. Cell densities obtained at differentfoaming temperatures are included. Lines are included to emphasize the transition at approximately 47 cm (STP)/cm (polymer). (Reprintedfrom reference 36. Copyright 2001 American Chemical Society.) 3

3


231 Table I. Chemical Structure, Mass Density, Glass Transition Temperature, and Dual Mode Sorption Parameters of C 0 for the PEI and PES Films at 25 °C. 2

Polyetherimide

T °C Mass density, g/cm Kp, cm (STP/cm (polymer)/bar C , cm (STP)/cm (polymer) bjbar

218 1.28 0.428 40.01 0.088

gJ

3

3

3

3

3

H


4

Polyethersulfone

230 136 0.265 45.11 0.126

Source: Reproduced from reference 36. Copyright 2001 American Chemical Society

Another example of foaming, while not immediately applicable to microelectronics due to large pores sizes, was a method by which microcellular materials were formed via self-assembly in CO2. This system used foaming in C 0 of hydrogen bonded small compounds and polymers to form low density, low thermal conductivity, microfibrillar foams. The precursors were nonpolymeric bisurea and trisurea compounds, acrylate copolymers, and fluorinated polyacrylate urea (Figure 6.) The behavior of the various compounds in C 0 reflected the self-association strength (number of physical cross-links points, strength of the interactions) versus the solute-C0 interaction strength. If selfassociation via hydrogen bonding was too strong, the material either did not dissolve in C 0 or precipitated as a powder. If self-association was too weak versus interaction with C 0 , the compound dissolved readily but required significant depressurization prior to precipitation, and the resulting foam exhibited relatively large cells (Figure 7.) The trisurea compounds (1) with a symmetric spacer in the hydrogen bond core and three association points per molecule, were found to provide the optimum structure to generate strong microcellular foams. 37

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Conclusions Nanoporous materials have become important for the next generation of ultralow-£ dielectrics for the microelectronics industry. Towards this goal a number of different methods have been developed to form such materials. One subset of these involve the use of scC0 as either a development solvent (i.e. extraction of a component) or as a foaming agent. Various (co-)polymers and additives have been tested to determine the best conditions which lead to nanoporous materials. Some of these materials and methods have resulted in low 2



232

2 m = 2, R = ~ÎCH )e— ,n = 8 2

5

m = 2, R = H C=CH(CH )C02(CH )2-- · 2

3

2

η

=

8

Figure 6. Synthesis of Urea compounds 1-5. Conditions: (i)EDCI, DMAPNBOC-Asp; (ii) TFA; (Hi) TEA, isocyanate. (Adaptedfrom reference 37)

Figure 7. SEM image of the foamfromtriurea compound lb in carbon dioxide from concentration of 0.1 wt %. (Reprintedfrom reference 37. Copyright 2002 American Chemical Society.)


233 dielectric constant materials. Further improvements, however, in reducing pore size and increasing material strength so as to form low-k materials for industrial applications are still necessary in order to replace the currently used porous silicates.

Acknowledgements Support for this work is provided in part by the Kenan Center for die Utilization of C 0 in Manufacturing and by the STC Program of the National Science Foundation under Agreement No. CHE-9876674. The authors acknowledge Dr. W. Ambrose and Dr. D. Bachelor for assistance with T E M and SEM, respectively.


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