(PDMS) Properties for Biomedical Micro/Nanosystems
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Biomedical Microdevices 7:4, 281–293, 2005 C 2005 Springer Science + Business Media, Inc. Manufactured in The Netherlands. Characterization of Polydimethylsiloxane (PDMS) Properties for Biomedical Micro/Nanosystems Alvaro Mata,1,2 Aaron J. Fleischman,2 and Shuvo Roy2,∗ 1Department of Chemical and Biomedical Engineering, Cleveland State University, Cleveland, OH 44115 2BioMEMS Laboratory, Department of Biomedical Engineering, Lerner Research Institute, The Cleveland Clinic Foundation, 9500 Euclid Avenue, Cleveland, OH 44120 E-mail: [email protected] Abstract. Polydimethylsiloxane (PDMS SylgardR 184, Dow Corn- search and development of MEMS-based devices in the ing Corporation) pre-polymer was combined with increasing biomedical arena for a variety of applications ranging amounts of cross-linker (5.7, 10.0, 14.3, 21.4, and 42.9 wt.%) and from diagnostics (Fujii, 2002; Mastrangelo et al., 1998; designated PDMS1, PDMS2, PDMS3, PDMS4, and PDMS5,respec- tively. These materials were processed by spin coating and subjected Paranjape et al., 2003; Wu et al., 2001) to therapeutics to common microfabrication, micromachining, and biomedical pro- (Borenstein et al., 2002; Chung et al., 2003; Ferrara et al., cesses: chemical immersion, oxygen plasma treatment, sterilization, 2003; Santini et al., 1999; Tao and Desai, 2003). However, and exposure to tissue culture media. The PDMS formulations were the development of these applications through established analyzed by gravimetry, goniometry, tensile testing, nanoindenta- MEMS manufacturing approaches is hindered by inherent tion, scanning electron microscopy (SEM), Fourier transform in- frared spectroscopy (FTIR), and X-ray photoelectron spectroscopy characteristics of traditional silicon-based processes such (XPS). Spin coating of PDMS was formulation dependent with film as high costs and limited access to clean room environ- thickness ranging from 308 µmonPDMS1 to 171 µmonPDMS5 ments (Roy et al., 2001; Whitesides et al., 2001). More- at 200 revolutions per minute (rpm). Ultimate tensile stress (UTS) over, the most successful silicon-based microfabrication increased from 3.9 MPa (PDMS1)to10.8 MPa (PDMS3), and then process has been photolithography, which is expensive, decreased down to 4.0 MPa (PDMS5). Autoclave sterilization (AS) increased the storage modulus (σ) and UTS in all formulations, with works for a limited set of materials, and is often limited the highest increase in UTS exhibited by PDMS5 (218%). PDMS sur- to planar surfaces (Deng et al., 2000; Quake and Scherer, face hydrophilicity and micro-textures were generally unaffected 2000; Xia and Whitesides, 1998). when exposed to the different chemicals, except for micro-texture The diversity of applications and commercialization of changes after immersion in potassium hydroxide and buffered hy- MEMS has encouraged the MEMS community to find pro- drofluoric, nitric, sulfuric, and hydrofluoric acids; and minimal changes in contact angle after immersion in hexane, hydrochloric cesses and materials that enable mass production while re- acid, photoresist developer, and toluene. Oxygen plasma treatment ducing costs. Likewise, the increasing number of biomed- decreased the contact angle of PDMS2 from 109◦ to 60◦. Exposure ical MEMS (BioMEMS) applications has led to a diver- to tissue culture media resulted in increased PDMS surface element gence from traditional silicon-based processing, and the concentrations of nitrogen and oxygen. pursuit of more biologically friendly materials. New fab- KeyWords. polydimethylsiloxane, PDMS, Poly(dimethylsiloxane), rication techniques such as Soft Lithography have fos- mechanical properties, micromachining, microfabrication, MEMS, tered the use of biocompatible materials such as polymers microsystems, contact angle, sterilization, tensile strength, struc- (Whitesides et al., 2001; Xia and Whitesides, 1998). The tural properties, nanotechnology, nanosystems practicability of polymers for fabrication with both rapid prototyping and mass production techniques as well as lower cost relative to silicon and glass make them partic- 1. Introduction ularly attractive for the development of BioMEMS (Deng et al., 2000; Quake and Scherer, 2000). Polycarbonate Recent advances in microelectromechanical systems (PC), polymethylmethacrylate (PMMA), polyvinylchlo- (MEMS) technology are providing new opportunities for ride (PVC), polyethylene (PE), and polydimethylsiloxane avariety of biological and medical applications (Bashir, (PDMS) are some of the polymer candidates for the low 2004; Rebello, 2004; Roy et al., 2001; Ziaie et al., 2004). cost, mass production of BioMEMS devices (Despa et al., Microfabrication and micromachining-based approaches 1999; Duffy et al., 1998; Lee et al., 2001; Lin et al., 1998; offer the potential to tackle biomedical problems within Weietal., 2005). the same size scale of cells and subcellular structures (Desai, 2000; Itoh, 1999; Kane et al., 1999; Mata et al., 2003). Consequently, there has been an increase in re- ∗Corresponding author. 281 282 Mata, Fleischman and Roy PDMS is a silicone elastomer with desirable properties and PDMS5, corresponding to 5.7, 10.0, 14.3, 21.4, and that make it attractive for the development of MEMS and 42.9 wt.% cross-linker, respectively. The different PDMS microfluidics components for biomedical applications (Jo formulations were formulated to investigate possible al- et al., 2000; Mata et al., 2002b; McDonald and White- terations in PDMS properties due to deviation from the sides, 2002; Unger et al., 2000). It is chemically inert, recommended 10:1 weight ratio, which corresponds to thermally stable, permeable to gases, simple to handle our PDMS2 notation. and manipulate, exhibits isotropic and homogeneous prop- The surface and structural properties of the different erties as well as lower cost than silicon, and can con- PDMS formulations were analyzed to investigate the ef- form to submicron features to develop microstructures fects of common biomedical, microfabrication, and mi- (McDonald and Whitesides, 2002; Ng et al., 2002; Xia and cromachining processes including: (a) spin coating—to Whitesides, 1998). The use of PDMS for BioMEMS appli- quantify the effect of the amount of cross-linker on thick- cations has been largely driven by the development of Soft ness profiles; (b) chemical immersion—to characterize Lithography techniques such as micro-contact printing, and quantify the effect of various chemicals used in micro- replica molding, micro-transfer molding, micro-molding fabrication and micromachining on both surface micro- in capillaries, and solvent-assisted micro-molding (Xia texture degradation and long-term surface hydrophilic- and Whitesides, 1998). These techniques usually require ity; (c) exposure to oxygen plasma—to quantify its effect the use of PDMS to create an elastomeric stamp or mold on long-term surface hydrophilicity; (d) sterilization—to that incorporates microstructures for transfer of patterns characterize and quantify the effect of various sterilization onto a subsequent substrate. In addition, PDMS is trans- procedures on surface micro-texture degradation, long- parent, non-fluorescent, biocompatible and nontoxic, and term surface hydrophilicity, surface chemical composi- has been traditionally used as a biomaterial in catheters, tion, and mechanical properties; and (e) exposure to tis- drainage tubing, insulation for pacemakers, membrane sue culture media—to characterize changes in the surface oxygenators, and ear and nose implants (Visser et al., chemical composition. The PDMS formulations were an- 1996). alyzed by gravimetry, goniometry, tensile testing, nanoin- The extensive biomaterial foundation of PDMS in dentation, scanning electron microscopy (SEM), X-ray conjunction with the increasing interest in low cost, photoelectron spectroscopy (XPS), and Fourier Transform mass-produced, microfabrication compatible, polymeric Infrared Spectroscopy (FTIR). Statistical significance was MEMS make it formidable and promising material for defined at the 95% confidence interval using a One Way current and future BioMEMS applications. Consequently, Analysis of Variance (ANOVA) test performed in Sigma- there is significant interest in examining the compatibil- Stat Statistical Software Version 2.0 (SPSS, Chicago, IL). ity of PDMS with both MEMS technology and biomedical A summary of the various processes and respective anal- applications. Therefore, we investigated the structural and ysis tools is presented in Table 1. It should be noted that surface properties of SylgardR 184 (Dow Corning Corpo- not all PDMS formulations were investigated for effects ration, Midland, MI), which is a widely used commer- of the different processes. The basis for choice of specific cially available brand of PDMS. This paper reports on the PDMS formulations for certain processes was based on effects of various biomedical, microfabrication, and mi- equipment availability. Nevertheless, PDMS2 was used in cromachining processes on the characteristics of PDMS all investigations since it is the standard formulation rec- SylgardR 184. More specifically, this paper attempts to ommended by the manufacturer. convey relevant information on particular properties of PDMS that will accelerate its wider adoption for the de- velopment of BioMEMS devices and applications. 2.2. Processes Spin coating. Spin coating is a common microfabrica- tion method for producing polymer films of controlled and 2. Materials and Methods uniform thickness (Linderholm and Asberg, 2000; Lotters et al.,